Polymerizable blockers of high energy light

ABSTRACT

Described are high energy light blocking compounds and ophthalmic devices containing the compounds. In particular, described are hydroxybiphenyl benzotriazole structures with polymerizable functionality that block high energy light and are visibly transparent. The hydroxybiphenyl benzotriazole structures can be incorporated into ophthalmic devices, such as hydrogel contact lenses, to protect eyes from high energy light radiation.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 62/524,760, filed Jun. 26, 2017, which is incorporated herein byreference in its entirety.

FIELD OF THE INVENTION

The invention relates to high energy light blockers. More particularly,the invention pertains to hydroxybiphenyl benzotriazole derivatives withpolymerizable functionality that block high energy light (includingultraviolet light) and are visibly transparent when incorporated in anarticle. Thus, the high energy light blockers may be used in polymericarticles, including biomedical devices, such as ophthalmic devices.

BACKGROUND OF THE INVENTION

High energy radiation from the sun, such as UV and high-energy visiblelight, is known to be responsible for cellular damage. While most of theradiation below 280 nm in wavelength is absorbed by the earth'satmosphere, photons possessing wavelengths ranging between 280 and 400nm have been associated with several ocular disorders including cornealdegenerative changes, and age related cataract and macular degeneration.(See Statement on Ocular Ultraviolet Radiation Hazards in Sunlight,American Optometric Association, Nov. 10, 1993). The human corneaabsorbs radiation up to 320 nm in wavelength (30% transmission) (Doutch,J. J., Quantock, A. J., Joyce, N.C., Meek, K. M, Biophys. J, 2012, 102,1258-1264), but is inefficient in protecting the back of the eye fromradiation ranging from 320 to 400 nm in wavelength.

Contact lens standards define the upper UV radiation wavelength at 380nm. The current Class I UV blocking criteria defined by the AmericanOptometric Association require >99% of the radiation between 280 and 315nm (UV B) and >90% of the 316 to 380 nm (UV A) radiation to be absorbedby the contact lens. While the criteria effectively address protectionof the cornea (<1% UV B transmittance), there is little attention paidto the lower energy UV radiation (>380<400 nm) and the high energyvisible radiation associated with retinal damage (Ham, W. T, Mueller, H.A., Sliney, D. H. Nature 1976; 260(5547):153-5).

Polymerizable compounds possessing appropriate chromophores, if used asophthalmic device monomers, can help protect the cornea, as well as theinterior cells in the ocular environment, from degradation caused byhigh energy light.

SUMMARY OF THE INVENTION

The invention relates to high energy light absorbers withhydroxybiphenyl benzotriazole structures having a high absorption (lowtransmission) over the wavelength range of at least 200-370 nm, whilesubstantially transmitting (e.g., greater than 80% transmission) atwavelengths longer than about 400 nm or longer than about 425 nm. Thematerials are therefore effective at blocking high energy light, such asUV (UVA and UVB) and, in some cases, high energy visible light (e.g., upto 400 nm or greater).

In one aspect, therefore, the invention provides a compound of formulaI:

wherein:

R¹ at each occurrence is independently H, halo, amino, or hydroxyl; and

at least one of R² or R³ is a group of formula R_(g)-L, wherein R_(g) isa polymerizable group and L is a linking group, and the remaining R² andR³ are independently at each occurrence R_(g)-L, H, C₁-C₆ alkyl, C₁-C₆alkoxy, or C₃-C₇ cycloalkyl;

wherein the alkyl and cycloalkyl groups may be unsubstituted orsubstituted.

The invention also provides an ophthalmic device comprising the compoundof formula I as a free radical reaction product.

The invention further provides a method for making an ophthalmic device.The method comprises: (a) providing a reactive mixture containing acompound of formula I, one or more monomers suitable for use in makingan ophthalmic device, and a radical initiator; and (b) polymerizing thereactive mixture to form the ophthalmic device.

The invention also provides a contact lens comprising a hydrogel polymerformed by polymerizing one or more monomers suitable for use in makingthe hydrogel polymer, and copolymerizing an effective amount of acompound of formula I.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows transmission spectra of 0.2 mM solutions of Norbloc,Compound (D), and Compound (K) in methanol.

FIG. 2 shows transmission Spectra of 0.2 mM solutions of Norbloc andCompound (M) in methylene chloride, and 1 mM Compound (M) in methylenechloride.

FIG. 3 shows transmission spectra of contact lenses made from siliconehydrogel Formulation 4A containing 0.619 mole percent of Compound (M)and silicone hydrogel Formulation 4B containing 0.619 mole percent ofNorbloc® in borate packaging solutions.

DETAILED DESCRIPTION OF THE INVENTION

It is to be understood that the invention is not limited to the detailsof construction or process steps set forth in the following description.The invention is capable of other embodiments and of being practiced orbeing carried out in various ways using the teaching herein.

As noted above, the invention provides high energy light blockers. Thehigh energy light blockers contain hydroxybiphenyl benzotriazole corestructures. The materials also contain polymerizable functionality. Ithas been discovered that such materials are capable of blocking highenergy light at more wavelengths than would be expected based on theblocking characteristics of known benzotriazole materials that do notcontain a hydroxybiphenyl moiety. In addition, some benzotriazolematerials that do not contain a hydroxybiphenyl moiety exhibit a window,in the range of about 250 to 280 nm, where UV blocking is reduced.Advantageously, compounds of the invention eliminate or significantlyreduce this window. Thus, materials according to the invention have beenfound to comprehensively block high energy light in the wavelength rangeof at least from 200 to 370 nm. Some hydroxybiphenyl benzotriazolematerials may block high energy light in the range of 200 to 380 nm, or200 to 390 nm, or 200 to 400 nm. Advantageously, the materials exhibit atransmission cut-off (e.g., they absorb 20 percent or less, preferably10 percent or less, more preferably 5% or less) at visible wavelengthslonger than about 400 nm or longer than about 425 nm. Thus, thematerials successfully block both UVA and UVB while transmitting in thevisible spectrum, making them strong Class I and Class II UV absorbersthat are well suited for use in ophthalmic applications.

With respect to the terms used in this disclosure, the followingdefinitions are provided.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which the invention belongs. The polymer definitions areconsistent with those disclosed in the Compendium of Polymer Terminologyand Nomenclature, IUPAC Recommendations 2008, edited by: Richard G.Jones, Jaroslav Kahovec, Robert Stepto, Edward S. Wilks, Michael Hess,Tatsuki Kitayama, and W. Val Metanomski. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference.

As used herein, the term “(meth)” designates optional methylsubstitution. Thus, a term such as “(meth)acrylates” denotes bothmethacrylates and acrylates.

Wherever chemical structures are given, it should be appreciated thatalternatives disclosed for the substituents on the structure may becombined in any combination. Thus, if a structure contained substituentsR* and R**, each of which contained three lists of potential groups, 9combinations are disclosed. The same applies for combinations ofproperties.

When a subscript, such as “n” in the generic formula [***]_(n), is usedto depict the number of repeating units in a polymer's chemical formula,the formula should be interpreted to represent the number averagemolecular weight of the macromolecule.

The term “individual” includes humans and vertebrates.

The term “biomedical device” refers to any article that is designed tobe used while either in or on mammalian tissues or fluids, andpreferably in or on human tissue or fluids. Examples of these devicesinclude but are not limited to wound dressings, sealants, tissuefillers, drug delivery systems, coatings, adhesion prevention barriers,catheters, implants, stents, and ophthalmic devices such as intraocularlenses and contact lenses. The biomedical devices may be ophthalmicdevices, particularly contact lenses, most particularly contact lensesmade from silicone hydrogels or conventional hydrogels.

The term “ocular surface” includes the surface and glandular epitheliaof the cornea, conjunctiva, lacrimal gland, accessory lacrimal glands,nasolacrimal duct and meibomian gland, and their apical and basalmatrices, puncta and adjacent or related structures, including eyelidslinked as a functional system by both continuity of epithelia, byinnervation, and the endocrine and immune systems.

The term “ophthalmic device” refers to any device which resides in or onthe eye or any part of the eye, including the ocular surface. Thesedevices can provide optical correction, cosmetic enhancement, visionenhancement, therapeutic benefit (for example as bandages) or deliveryof active components such as pharmaceutical and nutraceuticalcomponents, or a combination of any of the foregoing. Examples ofophthalmic devices include but are not limited to lenses, optical andocular inserts, including but not limited to punctal plugs, and thelike. “Lenses” include soft contact lenses, hard contact lenses, hybridcontact lenses, intraocular lenses, and overlay lenses. The ophthalmicdevice may comprise a contact lens.

The term “contact lens” refers to an ophthalmic device that can beplaced on the cornea of an individual's eye. The contact lens mayprovide corrective, cosmetic, or therapeutic benefit, including woundhealing, the delivery of drugs or nutraceuticals, diagnostic evaluationor monitoring, ultraviolet light blocking, visible light or glarereduction, or any combination thereof. A contact lens can be of anyappropriate material known in the art and can be a soft lens, a hardlens, or a hybrid lens containing at least two distinct portions withdifferent physical, mechanical, or optical properties, such as modulus,water content, light transmission, or combinations thereof.

The biomedical devices, ophthalmic devices, and lenses of the presentinvention may be comprised of silicone hydrogels or conventionalhydrogels. Silicone hydrogels typically contain at least one hydrophilicmonomer and at least one silicone-containing component that arecovalently bound to one another in the cured device.

“Target macromolecule” means the macromolecule being synthesized fromthe reactive monomer mixture comprising monomers, macromers,prepolymers, cross-linkers, initiators, additives, diluents, and thelike.

The term “polymerizable compound” means a compound containing one ormore polymerizable groups. The term encompasses, for instance, monomers,macromers, oligomers, prepolymers, cross-linkers, and the like.

“Polymerizable groups” are groups that can undergo chain growthpolymerization, such as free radical and/or cationic polymerization, forexample a carbon-carbon double bond which can polymerize when subjectedto radical polymerization initiation conditions. Non-limiting examplesof free radical polymerizable groups include (meth)acrylates, styrenes,vinyl ethers, (meth)acrylamides, N-vinyllactams, N-vinylamides,O-vinylcarbamates, O-vinylcarbonates, and other vinyl groups.Preferably, the free radical polymerizable groups comprise(meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinylamide, andstyryl functional groups, and mixtures of any of the foregoing. Morepreferably, the free radical polymerizable groups comprise(meth)acrylates, (meth)acrylamides, and mixtures thereof. Thepolymerizable group may be unsubstituted or substituted. For instance,the nitrogen atom in (meth)acrylamide may be bonded to a hydrogen, orthe hydrogen may be replaced with alkyl or cycloalkyl (which themselvesmay be further substituted).

Any type of free radical polymerization may be used including but notlimited to bulk, solution, suspension, and emulsion as well as any ofthe controlled radical polymerization methods such as stable freeradical polymerization, nitroxide-mediated living polymerization, atomtransfer radical polymerization, reversible addition fragmentation chaintransfer polymerization, organotellurium mediated living radicalpolymerization, and the like.

A “monomer” is a mono-functional molecule which can undergo chain growthpolymerization, and in particular, free radical polymerization, therebycreating a repeating unit in the chemical structure of the targetmacromolecule. Some monomers have di-functional impurities that can actas cross-linking agents. A “hydrophilic monomer” is also a monomer whichyields a clear single phase solution when mixed with deionized water at25° C. at a concentration of 5 weight percent. A “hydrophilic component”is a monomer, macromer, prepolymer, initiator, cross-linker, additive,or polymer which yields a clear single phase solution when mixed withdeionized water at 25° C. at a concentration of 5 weight percent. A“hydrophobic component” is a monomer, macromer, prepolymer, initiator,cross-linker, additive, or polymer which is slightly soluble orinsoluble in deionized water at 25° C.

A “macromolecule” is an organic compound having a number averagemolecular weight of greater than 1500, and may be reactive ornon-reactive.

A “macromonomer” or “macromer” is a macromolecule that has one groupthat can undergo chain growth polymerization, and in particular, freeradical polymerization, thereby creating a repeating unit in thechemical structure of the target macromolecule. Typically, the chemicalstructure of the macromer is different than the chemical structure ofthe target macromolecule, that is, the repeating unit of the macromer'spendent group is different than the repeating unit of the targetmacromolecule or its mainchain. The difference between a monomer and amacromer is merely one of chemical structure, molecular weight, andmolecular weight distribution of the pendent group. As a result, and asused herein, the patent literature occasionally defines monomers aspolymerizable compounds having relatively low molecular weights of about1,500 Daltons or less, which inherently includes some macromers. Inparticular, monomethacryloxypropyl terminated mono-n-butyl terminatedpolydimethylsiloxane (molecular weight=500-1500 g/mol) (mPDMS) andmono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminatedmono-n-butyl terminated polydimethylsiloxane (molecular weight=500-1500g/mol) (OH-mPDMS) may be referred to as monomers or macromers.Furthermore, the patent literature occasionally defines macromers ashaving one or more polymerizable groups, essentially broadening thecommon definition of macromer to include prepolymers. As a result and asused herein, di-functional and multi-functional macromers, prepolymers,and crosslinkers may be used interchangeably.

A “silicone-containing component” is a monomer, macromer, prepolymer,cross-linker, initiator, additive, or polymer in the reactive mixturewith at least one silicon-oxygen bond, typically in the form of siloxygroups, siloxane groups, carbosiloxane groups, and mixtures thereof.

Examples of silicone-containing components which are useful in thisinvention may be found in U.S. Pat. Nos. 3,808,178, 4,120,570,4,136,250, 4,153,641, 4,740,533, 5,034,461, 5,070,215, 5,244,981,5,314,960, 5,331,067, 5,371,147, 5,760,100, 5,849,811, 5,962,548,5,965,631, 5,998,498, 6,367,929, 6,822,016, 6,943,203, 6,951,894,7,052,131, 7,247,692, 7,396,890, 7,461,937, 7,468,398, 7,538,146,7,553,880, 7,572,841, 7,666,921, 7,691,916, 7,786,185, 7,825,170,7,915,323, 7,994,356, 8,022,158, 8,163,206, 8,273,802, 8,399,538,8,415,404, 8,420,711, 8,450,387, 8,487,058, 8,568,626, 8,937,110,8,937,111, 8,940,812, 8,980,972, 9,056,878, 9,125,808, 9,140,825,9,156,934, 9,170,349, 9,217,813, 9,244,196, 9,244,197, 9,260,544,9,297,928, 9,297,929, and European Patent No. 080539. These patents arehereby incorporated by reference in their entireties.

A “polymer” is a target macromolecule composed of the repeating units ofthe monomers used during polymerization.

A “homopolymer” is a polymer made from one monomer; a “copolymer” is apolymer made from two or more monomers; a “terpolymer” is a polymer madefrom three monomers. A “block copolymer” is composed of compositionallydifferent blocks or segments. Diblock copolymers have two blocks.Triblock copolymers have three blocks. “Comb or graft copolymers” aremade from at least one macromer.

A “repeating unit” is the smallest group of atoms in a polymer thatcorresponds to the polymerization of a specific monomer or macromer.

An “initiator” is a molecule that can decompose into radicals which cansubsequently react with a monomer to initiate a free radicalpolymerization reaction. A thermal initiator decomposes at a certainrate depending on the temperature; typical examples are azo compoundssuch as 1,1′-azobisisobutyronitrile and 4,4′-aobis(4-cyanovaleric acid),peroxides such as benzoyl peroxide, tert-butyl peroxide, tert-butylhydroperoxide, tert-butyl peroxybenzoate, dicumyl peroxide, and lauroylperoxide, peracids such as peracetic acid and potassium persulfate aswell as various redox systems. A photo-initiator decomposes by aphotochemical process; typical examples are derivatives of benzil,benzoin, acetophenone, benzophenone, camphorquinone, and mixturesthereof as well as various monoacyl and bisacyl phosphine oxides andcombinations thereof.

A “cross-linking agent” is a di-functional or multi-functional monomeror macromer which can undergo free radical polymerization at two or morelocations on the molecule, thereby creating branch points and apolymeric network. Common examples are ethylene glycol dimethacrylate,tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate,methylene bisacrylamide, triallyl cyanurate, and the like.

A “prepolymer” is a reaction product of monomers which containsremaining polymerizable groups capable of undergoing further reaction toform a polymer.

A “polymeric network” is a cross-linked macromolecule that can swell butcannot dissolve in solvents. “Hydrogels” are polymeric networks thatswell in water or aqueous solutions, typically absorbing at least 10weight percent water. “Silicone hydrogels” are hydrogels that are madefrom at least one silicone-containing component with at least onehydrophilic component. Hydrophilic components may also includenon-reactive polymers.

“Conventional hydrogels” refer to polymeric networks made fromcomponents without any siloxy, siloxane or carbosiloxane groups.Conventional hydrogels are prepared from reactive mixtures comprisinghydrophilic monomers. Examples include 2-hydroxyethyl methacrylate(“HEMA”), N-vinyl pyrrolidone (“NVP”), N, N-dimethylacrylamide (“DMA”)or vinyl acetate. U.S. Pat. Nos. 4,436,887, 4,495,313, 4,889,664,5,006,622, 5,039459, 5,236,969, 5,270,418, 5,298,533, 5,824,719,6,420,453, 6,423,761, 6,767,979, 7,934,830, 8,138,290, and 8,389,597disclose the formation of conventional hydrogels. Commercially availableconventional hydrogels include, but are not limited to, etafilcon,genfilcon, hilafilcon, lenefilcon, nesofilcon, omafilcon, polymacon, andvifilcon, including all of their variants.

“Silicone hydrogels” refer to polymeric networks made from at least onehydrophilic component and at least one silicone-containing component.Examples of silicone hydrogels include acquafilcon, asmofilcon,balafilcon, comfilcon, delefilcon, enfilcon, falcon, fanfilcon,formofilcon, galyfilcon, lotrafilcon, narafilcon, riofilcon, samfilcon,senofilcon, somofilcon, and stenfilcon, including all of their variants,as well as silicone hydrogels as prepared in U.S. Pat. Nos. 4,659,782,4,659,783, 5,244,981, 5,314,960, 5,331,067, 5,371,147, 5,998,498,6,087,415, 5,760,100, 5,776,999, 5,789,461, 5,849,811, 5,965,631,6,367,929, 6,822,016, 6,867,245, 6,943,203, 7,247,692, 7,249,848,7,553,880, 7,666,921, 7,786,185, 7,956,131, 8,022,158, 8,273,802,8,399,538, 8,470,906, 8,450,387, 8,487,058, 8,507,577, 8,637,621,8,703,891, 8,937,110, 8,937,111, 8,940,812, 9,056,878, 9,057,821,9,125,808, 9,140,825, 9,156,934, 9,170,349, 9,244,196, 9,244,197,9,260,544, 9,297,928, 9,297,929 as well as WO 03/22321, WO 2008/061992,and US 2010/0048847. These patents are hereby incorporated by referencein their entireties.

An “interpenetrating polymeric network” comprises two or more networkswhich are at least partially interlaced on the molecular scale but notcovalently bonded to each other and which cannot be separated withoutbraking chemical bonds. A “semi-interpenetrating polymeric network”comprises one or more networks and one or more polymers characterized bysome mixing on the molecular level between at least one network and atleast one polymer. A mixture of different polymers is a “polymer blend.”A semi-interpenetrating network is technically a polymer blend, but insome cases, the polymers are so entangled that they cannot be readilyremoved.

The terms “reactive mixture” and “reactive monomer mixture” refer to themixture of components (both reactive and non-reactive) which are mixedtogether and when subjected to polymerization conditions form theconventional or silicone hydrogels of the present invention as well ascontact lenses made therefrom. The reactive monomer mixture may comprisereactive components such as the monomers, macromers, prepolymers,cross-linkers, and initiators, additives such as wetting agents, releaseagents, polymers, dyes, light absorbing compounds such as UV absorbers,pigments, dyes and photochromic compounds, any of which may be reactiveor non-reactive but are capable of being retained within the resultingbiomedical device, as well as pharmaceutical and nutraceuticalcompounds, and any diluents. It will be appreciated that a wide range ofadditives may be added based upon the biomedical device which is madeand its intended use. Concentrations of components of the reactivemixture are expressed as weight percentages of all components in thereactive mixture, excluding diluent. When diluents are used, theirconcentrations are expressed as weight percentages based upon the amountof all components in the reactive mixture and the diluent.

“Reactive components” are the components in the reactive mixture whichbecome part of the chemical structure of the polymeric network of theresulting hydrogel by covalent bonding, hydrogen bonding, electrostaticinteractions, the formation of interpenetrating polymeric networks, orany other means.

The term “silicone hydrogel contact lens” refers to a contact lenscomprising at least one silicone hydrogel. Silicone hydrogel contactlenses generally have increased oxygen permeability compared toconventional hydrogels. Silicone hydrogel contact lenses use both theirwater and polymer content to transmit oxygen to the eye.

The term “multi-functional” refers to a component having two or morepolymerizable groups. The term “mono-functional” refers to a componenthaving one polymerizable group.

The terms “halogen” or “halo” indicate fluorine, chlorine, bromine, andiodine.

As used herein, the term “alkyl” refers to an unsubstituted orsubstituted linear or branched alkyl group containing the indicatednumber of carbon atoms. If no number is indicated, then alkyl(optionally including any substituents on alkyl) may contain 1 to 16carbon atoms. Preferably, the alkyl group contains 1 to 10 carbon atoms,alternatively 1 to 7 carbon atoms, or alternatively 1 to 4 carbon atoms.Examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, iso-,sec- and tert-butyl, pentyl, hexyl, heptyl, 3-ethylbutyl, and the like.Examples of substituents on alkyl include 1, 2, or 3 groupsindependently selected from hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halogen, phenyl,benzyl, and combinations thereof. “Alkylene” means a divalent alkylgroup, such as —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂CH(CH₃)CH₂—, and—CH₂CH₂CH₂CH₂—.

“Haloalkyl” refers to an alkyl group as defined above substituted withone or more halogen atoms, where each halogen is independently F, Cl, Bror I. A preferred halogen is F. Preferred haloalkyl groups contain 1-6carbons, more preferably 1-4 carbons, and still more preferably 1-2carbons. “Haloalkyl” includes perhaloalkyl groups, such as —CF₃— or—CF₂CF₃—. “Haloalkylene” means a divalent haloalkyl group, such as—CH₂CF₂—.

“Cycloalkyl” refers to an unsubstituted or substituted cyclichydrocarbon containing the indicated number of ring carbon atoms. If nonumber is indicated, then cycloalkyl may contain 3 to 12 ring carbonatoms. Preferred are C₃-C₈ cycloalkyl groups, C₃-C₇ cycloalkyl, morepreferably C₄-C₇ cycloalkyl, and still more preferably C₅-C₆ cycloalkyl.Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl and cyclooctyl. Examples of substituents oncycloalkyl include 1, 2, or 3 groups independently selected from alkyl,hydroxy, amino, amido, oxa, carbonyl, alkoxy, amido, carbamate,carbonate, halo, phenyl, benzyl, and combinations thereof“Cycloalkylene” means a divalent cycloalkyl group, such as1,2-cyclohexylene, 1,3-cyclohexylene, or 1,4-cyclohexylene.

“Heterocycloalkyl” refers to a cycloalkyl ring or ring system as definedabove in which at least one ring carbon has been replaced with aheteroatom selected from nitrogen, oxygen, and sulfur. Theheterocycloalkyl ring is optionally fused to or otherwise attached toother heterocycloalkyl rings and/or non-aromatic hydrocarbon ringsand/or phenyl rings. Preferred heterocycloalkyl groups have from 5 to 7members. More preferred heterocycloalkyl groups have 5 or 6 members.Heterocycloalkylene means a divalent heterocycloalkyl group.

“Aryl” refers to an unsubstituted or substituted aromatic hydrocarbonring system containing at least one aromatic ring. The aryl groupcontains the indicated number of ring carbon atoms. If no number isindicated, then aryl may contain 6 to 14 ring carbon atoms. The aromaticring may optionally be fused or otherwise attached to other aromatichydrocarbon rings or non-aromatic hydrocarbon rings. Examples of arylgroups include phenyl, naphthyl, and biphenyl. Preferred examples ofaryl groups include phenyl. Examples of substituents on aryl include 1,2, or 3 groups independently selected from alkyl, hydroxy, amino, amido,oxa, carboxy, alkyl carboxy, carbonyl, alkoxy, amido, carbamate,carbonate, halo, phenyl, benzyl, and combinations thereof. “Arylene”means a divalent aryl group, for example 1,2-phenylene, 1,3-phenylene,or 1,4-phenylene.

“Heteroaryl” refers to an aryl ring or ring system, as defined above, inwhich at least one ring carbon atom has been replaced with a heteroatomselected from nitrogen, oxygen, and sulfur. The heteroaryl ring may befused or otherwise attached to one or more heteroaryl rings, aromatic ornonaromatic hydrocarbon rings or heterocycloalkyl rings. Examples ofheteroaryl groups include pyridyl, furyl, and thienyl. “Heteroarylene”means a divalent heteroaryl group.

“Alkoxy” refers to an alkyl group attached to the parent molecularmoiety through an oxygen bridge. Examples of alkoxy groups include, forinstance, methoxy, ethoxy, propoxy and isopropoxy. “Aryloxy” refers toan aryl group attached to a parent molecular moiety through an oxygenbridge. Examples include phenoxy. “Cyclic alkoxy” means a cycloalkylgroup attached to the parent moiety through an oxygen bridge.

“Alkylamine” refers to an alkyl group attached to the parent molecularmoiety through an —NH bridge. Alkyleneamine means a divalent alkylaminegroup, such as —CH₂CH₂NH—.

“Siloxanyl” refers to a structure having at least one Si—O—Si bond.Thus, for example, siloxanyl group means a group having at least oneSi—O—Si group (i.e. a siloxane group), and siloxanyl compound means acompound having at least one Si—O—Si group. “Siloxanyl” encompassesmonomeric (e.g., Si—O—Si) as well as oligomeric/polymeric structures(e.g., —[Si—O]_(n)—, where n is 2 or more). Each silicon atom in thesiloxanyl group is substituted with independently selected R^(A) groups(where R^(A) is as defined in formula A options (b)-(i)) to completetheir valence.

“Silyl” refers to a structure of formula R₃Si— and “siloxy” refers to astructure of formula R₃Si—O—, where each R in silyl or siloxy isindependently selected from trimethylsiloxy, C₁-C₈ alkyl (preferablyC₁-C₃ alkyl, more preferably ethyl or methyl), and C₃-C₈ cycloalkyl.

“Alkyleneoxy” refers to groups of the general formula -(alkylene-O)_(p)—or —(O-alkylene)_(p)-, wherein alkylene is as defined above, and p isfrom 1 to 200, or from 1 to 100, or from 1 to 50, or from 1 to 25, orfrom 1 to 20, or from 1 to 10, wherein each alkylene is independentlyoptionally substituted with one or more groups independently selectedfrom hydroxyl, halo (e.g., fluoro), amino, amido, ether, carbonyl,carboxyl, and combinations thereof. If p is greater than 1, then eachalkylene may be the same or different and the alkyleneoxy may be inblock or random configuration. When alkyleneoxy forms a terminal groupin a molecule, the terminal end of the alkyleneoxy may, for instance, bea hydroxy or alkoxy (e.g., HO—[CH₂CH₂O]_(p)— or CH₃O—[CH₂CH₂O]_(p)—).Examples of alkyleneoxy include polymethyleneoxy, polyethyleneoxy,polypropyleneoxy, polybutyleneoxy, andpoly(ethyleneoxy-co-propyleneoxy).

“Oxaalkylene” refers to an alkylene group as defined above where one ormore non-adjacent CH₂ groups have been substituted with an oxygen atom,such as —CH₂CH₂OCH(CH₃)CH₂—. “Thiaalkylene” refers to an alkylene groupas defined above where one or more non-adjacent CH₂ groups have beensubstituted with a sulfur atom, such as —CH₂CH₂SCH(CH₃)CH₂—.

The term “linking group” refers to a moiety that links the polymerizablegroup to the parent molecule. The linking group may be any moiety thatdoes not undesirably interfere with the polymerization of the compoundof which it is a part. For instance, the linking group may be a bond, orit may comprise one or more alkylene, haloalkylene, amide, amine,alkyleneamine, carbamate, carboxylate (—CO₂—), arylene, heteroarylene,cycloalkylene, heterocycloalkylene, alkyleneoxy, oxaalkylene,thiaalkylene, haloalkyleneoxy (alkyleneoxy substituted with one or morehalo groups, e.g., —OCF₂—, —OCF₂CF₂—, —OCF₂CH₂—), siloxanyl,alkylenesiloxanyl, or combinations thereof. The linking group mayoptionally be substituted with 1 or more substituent groups. Suitablesubstituent groups may include those independently selected from alkyl,halo (e.g., fluoro), hydroxyl, HO-alkyleneoxy, MeO-alkyleneoxy,siloxanyl, siloxy, siloxy-alkyleneoxy-, siloxy-alkylene-alkyleneoxy-(where more than one alkyleneoxy groups may be present and wherein eachmethylene in alkylene and alkyleneoxy is independently optionallysubstituted with hydroxyl), ether, amine, carbonyl, carbamate, andcombinations thereof. The linking group may also be substituted with apolymerizable group, such as (meth)acrylate (in addition to thepolymerizable group to which the linking group is linked).

Preferred linking groups include C₁-C₈ alkylene (preferably C₂-C₆alkylene) and C₁-C₈ oxaalkylene (preferably C₂-C₆ oxaalkylene), each ofwhich is optionally substituted with 1 or 2 groups independentlyselected from hydroxyl and siloxy. Preferred linking groups also includecarboxylate, amide, C₁-C₈ alkylene-carboxylate-C₁-C₈ alkylene, or C₁-C₈alkylene-amide-C₁-C₈ alkylene.

When the linking group is comprised of combinations of moieties asdescribed above (e.g., alkylene and cycloalkylene), the moieties may bepresent in any order. For instance, if in Formula E below, L isindicated as being -alkylene-cycloalkylene-, then Rg-L may be eitherRg-alkylene-cycloalkylene-, or Rg-cycloalkylene-alkylene-.Notwithstanding this, the listing order represents the preferred orderin which the moieties appear in the compound starting from the terminalpolymerizable group (Rg) to which the linking group is attached. Forexample, if in Formula E, L and L² are indicated as both beingalkylene-cycloalkylene, then Rg-L is preferablyRg-alkylene-cycloalkylene- and -L²-Rg is preferably-cycloalkylene-alkylene-Rg.

The terms “high energy light blocker” or “high energy light absorber”refer to chemical materials which block ultraviolet light and, in somecases, also block high energy visible light. Thus, high energy lightblockers according to the invention block light at least in the range of200 to 370 nm. Some materials may block longer wavelengths of light(e.g., from 370 to 400 nm), thus, for instance, absorbing in the 200 to380 nm range, or the 200 to 390 nm range, or the 200 to 400 nm range. Ifthe amount of a material's blocking is indicated as a percentage for aparticular wavelength range, it is to be understood that the materialexhibits the percent blocking at all wavelengths within that range.Percent blocking at a particular wavelength can be determined from thematerial's transmission spectrum, where blocking=100−percenttransmission (% T). Preferred materials block at least 70%, or at least80%, or at least 85%, or at least 90%, or at least 95% of high energylight at all wavelengths within the indicated high energy light range,while significantly transmitting light in the visible range, thusallowing the materials to be used in ophthalmic applications. Preferredmaterials block 20% or less, preferably 10% or less, more preferably 5%or less in the visible spectrum, for instance from 400 nm to 700 nm, orfrom 425 nm to 700 nm.

Unless otherwise indicated, ratios, percentages, parts, and the like areby weight.

Unless otherwise indicated, numeric ranges, for instance as in “from 2to 10,” are inclusive of the numbers defining the range (e.g., 2 and10).

As noted above, in one aspect, the invention provides hydroxybiphenylbenzotriazole materials that function as high energy light blockers. Thehydroxybiphenyl benzotriazole materials are of the formula I:

wherein:

R¹ at each occurrence is independently H, halo, amino, or hydroxyl; and

at least one of R² or R³ is a group of formula R_(g)-L, wherein R_(g) isa polymerizable group and L is a linking group, and the remaining R² andR³ are independently at each occurrence R_(g)-L, H, C₁-C₆ alkyl, C₁-C₆alkoxy, or C₃-C₇ cycloalkyl, wherein the alkyl and cycloalkyl groups maybe unsubstituted or substituted. Hydroxybiphenyl benzotriazoles ofFormula I preferably contain one or two Rg-L groups. More preferably,the materials contain one Rg-L group.

Formula I-1.

Hydroxybiphenyl benzotriazoles of formula I may include materials offormula I-1, which are hydroxybiphenyl benzotriazoles of formula Iwherein R¹ is independently at each occurrence H or halogen. Preferredmaterials of formula I-1 include those wherein one R¹ is halo(preferably chloro) and the remaining R¹ are each hydrogen. Preferredmaterials of formula I-1 also include those wherein each R¹ is hydrogen.

I-2.

Hydroxybiphenyl benzotriazoles of formulae I and I-1 may includematerials of formula I-2, which are hydroxybiphenyl benzotriazoles offormula I or I-1 wherein R² and R³ at each occurrence are independentlyH, C₁-C₆ alkyl, or Rg-L. Preferred materials of formula I-2 includethose wherein one of the R² and R³ groups is Rg-L and the remaining R²and R³ groups are independently hydrogen or C₁-C₆ alkyl. Preferredmaterials of formula I-2 also include those wherein one of the R² and R³groups is Rg-L, one of the R² and R³ groups is C₁-C₆ alkyl (e.g.,t-butyl), and the remaining R² and R³ groups each are hydrogen.Preferred materials of formula I-2 further include those wherein one ofthe R² and R³ groups is Rg-L and the remaining R² and R³ groups are eachhydrogen.

I-3.

Hydroxybiphenyl benzotriazoles of formulae I, I-1, and I-2 may includematerials of formula I-3, which are hydroxybiphenyl benzotriazoles offormula I, I-1, or I-2 wherein Rg (the polymerizable group) at eachoccurrence independently comprises styryl, vinyl carbonate, vinyl ether,vinyl carbamate, N-vinyl lactam, N-vinylamide, (meth)acrylate, or(meth)acrylamide. The polymerizable group allows the hydroxybiphenylbenzotriazole materials of the invention to form covalent bonds whenreacted with monomers, crosslinking agents, and other componentsgenerally used in making polymeric devices. The compatibility of thehydroxybiphenyl benzotriazoles with the reactive mixture can becontrolled via the selection of the polymerizable group (and the linkinggroup). Preferred Rg groups include (meth)acrylate or (meth)acrylamide.A more preferred Rg group is methacrylate.

I-4.

Hydroxybiphenyl benzotriazoles of formulae I, I-1, I-2, and I-3 mayinclude materials of formula I-4, which are hydroxybiphenylbenzotriazoles of formula I, I-1, I-2, or I-3 wherein the linking groupcomprises C₁-C₈ alkylene (preferably C₂-C₆ alkylene), C₁-C₈ oxaalkylene(preferably C₂-C₆ oxaalkylene), C₁-C₈ thiaalkylene (preferably C₂-C₆thiaalkylene), C₁-C₈ alkylene-carboxylate-C₁-C₈ alkylene, C₁-C₈alkylene-amide-C₁-C₈ alkylene, or C₁-C₈ alkylene-amine-C₁-C₈ alkylene.Preferred linking groups may have the structure —[CH₂]_(m)—Y—[CH₂]_(n)—,wherein m is a number from 1 to 6; n is a number from 1 to 6; Y isabsent, or is O, S, C(═O)O, NR₅, or C(═O)NR₅, wherein R₅ is H or C₁-C₄alkyl. Particularly preferred linking groups are—CH₂CH₂—NH—C(═O)—CH₂CH₂— and —CH₂CH₂—O—C(═O)—CH₂CH₂—.

I-5.

Hydroxybiphenyl benzotriazoles of formulae I, I-1, I-2, I-3, and I-4 mayinclude materials of formula I-5, which are hydroxybiphenylbenzotriazoles of formula I, I-1, I-2, I-3, or I-4 having the structure:

wherein R¹, R², and R³ are as defined in formula I or its varioussub-formulae (I-I, I-2, I-3, or I-4).

I-6.

Hydroxybiphenyl benzotriazoles of formulae I, I-1, I-2, I-3, I-4, andI-5 may include materials of formula I-6, which are hydroxybiphenylbenzotriazoles of formula I, I-1, I-2, I-3, I-4, or I-5 having thestructure:

wherein R¹, R², and R³ are as defined in formula I or its varioussub-formulae (I-I, I-2, I-3, or I-4).

Examples of Hydroxybiphenyl benzotriazoles suitable for use in theinvention include, but are not limited to, compounds listed in Table 1.

TABLE 1

  2-((3-(5-(2H-benzo[d][1,2,3]triazol-2-yl)-6-hydroxy-[1,1′-biphenyl]-3-yl)propanoyl)oxy)ethyl methacrylate (Compound D)

  2-(3-(5-(2H-benzo[d][1,2,3]triazol-2-yl)-6-hydroxy-[1,1′-biphenyl]-3-yl)propanamido)ethyl methacrylate

  2-(3-(3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanamido)ethyl methacrylate (Compound K)

  2-(3-(5′-(tert-butyl)-3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanamido)ethyl methacrylate (CompoundM)

Compounds of formula I may be prepared as shown in the followingreaction scheme 1 and the associated description, as well as relevantliterature procedures that may be used by one of skill in the art.Exemplary reagents and procedures for these reactions appear in theworking examples.

Scheme 1 shows a method for preparing compounds of general formula I.Thus, Hydroxybiphenyl benzotriazoles can be formed by a Suzuki couplingreaction between a dioxaborolane derivative of a hydroxyphenylbenzotriazole with iodobenzene using for examplebis(triphenylphosphine)palladium(II) dichloride and potassium carbonate.The dioxaborolane derivative can be synthesized from the correspondinghydroxyl-bromo-phenyl benzotriazole using for example4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane), potassiumacetate, and [1,11-bis(diphenylphosphino)ferrocene]dichloropalladium(II).

The present invention encompasses compounds that may be used asprecursors from which the compounds of formula I may be prepared. Theseinclude:

As discussed above, the hydroxybiphenyl benzotriazoles of formula I areeffective at blocking high energy light in at least the 200-370 nm rangewhile transmitting visible wavelengths longer than about 400 nm orlonger than about 425 nm. Because of their selective high energy lightblocking properties, the compositions are well suited for use inophthalmic devices. In such devices, the compositions may block harmfulhigh energy radiation, therefore protecting the eye from damage, whileallowing transmission of visible light.

The hydroxybiphenyl benzotriazoles of formula I may be included inreactive mixtures to form an ophthalmic device. Generally, thehydroxybiphenyl benzotriazoles can be present in any amount up to thelimit of their solubility. For instance, the hydroxybiphenylbenzotriazoles may be present in an amount in the range of about 0.1% toabout 10% by weight, or from about 0.5 to about 5% by weight, or fromabout 0.75% to about 4% by weight. The upper limit is typicallydetermined by the solubility of the compound with other comonomers andor diluents in the reactive monomer mix.

A variety of ophthalmic devices containing the hydroxybiphenylbenzotriazoles of the invention may be prepared, including hard contactlenses, soft contact lenses, corneal onlays, corneal inlays, intraocularlenses, or overlay lenses. Preferably, the ophthalmic device is a softcontact lens, which may be made from conventional or silicone hydrogelformulations.

Ophthalmic devices may be prepared by polymerizing a reactive mixturecontaining the hydroxybiphenyl benzotriazole, one or more monomerssuitable for making the desired ophthalmic device, and optionalcomponents. Thus, the reactive mixture may include, in addition to ahydroxybiphenyl benzotriazole compound as described above, one or moreof: hydrophilic components, hydrophobic components, silicone-containingcomponents, wetting agents such as polyamides, crosslinking agents, andfurther components such as diluents and initiators.

Hydrophilic Components

Examples of suitable families of hydrophilic monomers include(meth)acrylates, styrenes, vinyl ethers, (meth)acrylamides, N-vinyllactams, N-vinyl amides, N-vinyl imides, N-vinyl ureas, 0-vinylcarbamates, 0-vinyl carbonates, other hydrophilic vinyl compounds, andmixtures thereof.

Non-limiting examples of hydrophilic (meth)acrylate and (meth)acrylamidemonomers include: acrylamide, N-isopropyl acrylamide,N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl acrylamide (DMA),2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl (meth)acrylate,3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate,2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate,4-hydroxybutyl (meth)acrylate, N-(2-hydroxyethyl) (meth)acrylamide,N,N-bis(2-hydroxyethyl) (meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N,N-bis(2-hydroxypropyl) (meth)acrylamide,N-(3-hydroxypropyl) (meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl) (meth)acrylamide,N-(4-hydroxybutyl) (meth)acrylamide, 2-aminoethyl (meth)acrylate,3-aminopropyl (meth)acrylate, 2-aminopropyl (meth)acrylate,N-2-aminoethyl (meth)acrylamides), N-3-aminopropyl (meth)acrylamide,N-2-aminopropyl (meth)acrylamide, N,N-bis-2-aminoethyl(meth)acrylamides, N,N-bis-3-aminopropyl (meth)acrylamide),N,N-bis-2-aminopropyl (meth)acrylamide, glycerol methacrylate,polyethyleneglycol monomethacrylate, (meth)acrylic acid, vinyl acetate,acrylonitrile, and mixtures thereof.

Hydrophilic monomers may also be ionic, including anionic, cationic,zwitterions, betaines, and mixtures thereof. Non-limiting examples ofsuch charged monomers include (meth)acrylic acid,N-[(ethenyloxy)carbonyl]-β-alanine (VINAL), 3-acrylamidopropanoic acid(ACA1), 5-acrylamidopentanoic acid (ACA2), 3-acrylamido-3-methylbutanoicacid (AMBA), 2-(methacryloyloxy)ethyl trimethylammonium chloride (Q Saltor METAC), 2-acrylamido-2-methylpropane sulfonic acid (AMPS),1-propanaminium,N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-, innersalt (CBT), 1-propanaminium,N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-, innersalt (SBT), 3,5-Dioxa-8-aza-4-phosphaundec-10-en-1-aminium,4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide (9CI) (PBT),2-methacryloyloxyethyl phosphorylcholine,3-(dimethyl(4-vinylbenzyl)ammonio)propane-1-sulfonate (DMVBAPS),3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate (AMPDAPS),3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate(MAMPDAPS),3-((3-(acryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (APDAPS),and methacryloyloxy)propyl)dimethylammonio)propane-1-sulfonate(MAPDAPS).

Non-limiting examples of hydrophilic N-vinyl lactam and N-vinyl amidemonomers include: N-vinyl pyrrolidone (NVP), N-vinyl-2-piperidone,N-vinyl-2-caprolactam, N-vinyl-3-methyl-2-caprolactam,N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone,N-vinyl-4-methyl-2-caprolactam, N-vinyl-3-ethyl-2-pyrrolidone,N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl acetamide (NVA),N-vinyl-N-methylacetamide (VMA), N-vinyl-N-ethyl acetamide,N-vinyl-N-ethyl formamide, N-vinyl formamide,N-vinyl-N-methylpropionamide, N-vinyl-N-methyl-2-methylpropionamide,N-vinyl-2-methylpropionamide, N-vinyl-N,N′-dimethylurea,1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone,5-methyl-3-methylene-2-pyrrolidone; 1-ethyl-5-methylene-2-pyrrolidone,N-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone,1-N-propyl-3-methylene-2-pyrrolidone,1-N-propyl-5-methylene-2-pyrrolidone,1-isopropyl-3-methylene-2-pyrrolidone,1-isopropyl-5-methylene-2-pyrrolidone, N-vinyl-N-ethyl acetamide,N-vinyl-N-ethyl formamide, N-vinyl formamide, N-vinyl isopropylamide,N-vinyl caprolactam, N-vinylimidazole, and mixtures thereof

Non-limiting examples of hydrophilic 0-vinyl carbamates and O-vinylcarbonates monomers include N-2-hydroxyethyl vinyl carbamate andN-carboxy-β-alanine N-vinyl ester. Further examples of hydrophilic vinylcarbonate or vinyl carbamate monomers are disclosed in U.S. Pat. No.5,070,215. Hydrophilic oxazolone monomers are disclosed in U.S. Pat. No.4,910,277.

Other hydrophilic vinyl compounds include ethylene glycol vinyl ether(EGVE), di(ethylene glycol) vinyl ether (DEGVE), allyl alcohol, and2-ethyl oxazoline.

The hydrophilic monomers may also be macromers or prepolymers of linearor branched poly(ethylene glycol), poly(propylene glycol), orstatistically random or block copolymers of ethylene oxide and propyleneoxide, having polymerizable moieties such as (meth)acrylates, styrenes,vinyl ethers, (meth)acrylamides, N-vinylamides, and the like. Themacromers of these polyethers have one polymerizable group; theprepolymers may have two or more polymerizable groups.

The preferred hydrophilic monomers of the present invention are DMA,NVP, HEMA, VMA, NVA, and mixtures thereof. Other suitable hydrophilicmonomers will be apparent to one skilled in the art.

Generally, there are no particular restrictions with respect to theamount of the hydrophilic monomer present in the reactive monomermixture. The amount of the hydrophilic monomers may be selected basedupon the desired characteristics of the resulting hydrogel, includingwater content, clarity, wettability, protein uptake, and the like.Wettability may be measured by contact angle, and desirable contactangles are less than about 100°, less than about 80°, and less thanabout 60°. The hydrophilic monomer may be present in an amount in therange of about 0.1 to about 80 weight percent, including in the range ofabout 5 to about 65 weight percent, and in the range of about 10 toabout 45 weight percent, based on the total weight of the reactivecomponents in the reactive monomer mixture.

Silicone-Containing Components

Silicone-containing components suitable for use in the inventioncomprise one or more polymerizable compounds, where each compoundindependently comprises at least one polymerizable group, at least onesiloxane group, and one or more linking groups connecting thepolymerizable group(s) to the siloxane group(s). The silicone-containingcomponents may, for instance, contain from 1 to 220 siloxane repeatunits, such as the groups defined below. The silicone-containingcomponent may also contain at least one fluorine atom.

The silicone-containing component may comprise: one or morepolymerizable groups as defined above; one or more optionally repeatingsiloxane units; and one or more linking groups connecting thepolymerizable groups to the siloxane units. The silicone-containingcomponent may comprise: one or more polymerizable groups that areindependently a (meth)acrylate, a styryl, a vinyl ether, a(meth)acrylamide, an N-vinyl lactam, an N-vinylamide, anO-vinylcarbamate, an O-vinylcarbonate, a vinyl group, or mixtures of theforegoing; one or more optionally repeating siloxane units; and one ormore linking groups connecting the polymerizable groups to the siloxaneunits.

The silicone-containing component may comprise: one or morepolymerizable groups that are independently a (meth)acrylate, a(meth)acrylamide, an N-vinyl lactam, an N-vinylamide, a styryl, ormixtures of the foregoing; one or more optionally repeating siloxaneunits; and one or more linking groups connecting the polymerizablegroups to the siloxane units.

The silicone-containing component may comprise: one or morepolymerizable groups that are independently a (meth)acrylate, a(meth)acrylamide, or mixtures of the foregoing; one or more optionallyrepeating siloxane units; and one or more linking groups connecting thepolymerizable groups to the siloxane units.

Formula A. The silicone-containing component may comprise one or morepolymerizable compounds of Formula A:

wherein:

at least one R^(A) is a group of formula R_(g)-L- wherein R_(g) is apolymerizable group and L is a linking group, and the remaining R^(A)are each independently:

-   -   (a) R_(g)-L-,    -   (b) C₁-C₁₆ alkyl optionally substituted with one or more        hydroxy, amino, amido, oxa, carboxy, alkyl carboxy, carbonyl,        alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or        combinations thereof,    -   (c) C₃-C₁₂ cycloalkyl optionally substituted with one or more        alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, amido,        carbamate, carbonate, halo, phenyl, benzyl, or combinations        thereof,    -   (d) a C₆-C₁₄ aryl group optionally substituted with one or more        alkyl, hydroxy, amino, amido, oxa, carboxy, alkyl carboxy,        carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl,        benzyl, or combinations thereof,    -   (e) halo,    -   (f) alkoxy, cyclic alkoxy, or aryloxy,    -   (g) siloxy,    -   (h) alkyleneoxy-alkyl or alkoxy-alkyleneoxy-alkyl, such as        polyethyleneoxyalkyl, polypropyleneoxyalkyl, or        poly(ethyleneoxy-co-propyleneoxyalkyl), or    -   (i) a monovalent siloxane chain comprising from 1 to 100        siloxane repeat units optionally substituted with alkyl, alkoxy,        hydroxy, amino, oxa, carboxy, alkyl carboxy, alkoxy, amido,        carbamate, halo or combinations thereof; and

n is from 0 to 500 or from 0 to 200, or from 0 to 100, or from 0 to 20,where it is understood that when n is other than 0, n is a distributionhaving a mode equal to a stated value. When n is 2 or more, the SiOunits may carry the same or different R^(A) substituents and ifdifferent R^(A) substituents are present, the n groups may be in randomor block configuration.

In Formula A, three R^(A) may each comprise a polymerizable group,alternatively two R^(A) may each comprise a polymerizable group, oralternatively one R^(A) may comprise a polymerizable group.

Formula B.

The silicone-containing component of formula A may be a mono-functionalpolymerizable compound of formula B:

wherein:

Rg is a polymerizable group;

L is a linking group;

j1 and j2 are each independently whole numbers from 0 to 220, providedthat the sum of j1 and j2 is from 1 to 220;

R^(A1), R^(A2), R^(A3), R^(A4), R^(A5), and R^(A7) are independently ateach occurrence C₁-C₆ alkyl, C₃-C₁₂ cycloalkyl, C₁-C₆ alkoxy, C₄-C₁₂cyclic alkoxy, alkoxy-alkyleneoxy-alkyl, aryl (e.g., phenyl), aryl-alkyl(e.g., benzyl), haloalkyl (e.g., partially or fully fluorinated alkyl),siloxy, fluoro, or combinations thereof, wherein each alkyl in theforegoing groups is optionally substituted with one or more hydroxy,amino, amido, oxa, carboxy, alkyl carboxy, carbonyl, alkoxy, carbamate,carbonate, halo, phenyl, or benzyl, each cycloalkyl is optionallysubstituted with one or more alkyl, hydroxy, amino, amido, oxa,carbonyl, alkoxy, carbamate, carbonate, halo, phenyl, or benzyl and eacharyl is optionally substituted with one or more alkyl, hydroxy, amino,amido, oxa, carboxy, alkyl carboxy, carbonyl, alkoxy, carbamate,carbonate, halo, phenyl, or benzyl; and

R^(A6) is siloxy, C₁-C₈ alkyl (e.g., C₁-C₄ alkyl, or butyl, or methyl),or aryl (e.g., phenyl), wherein alkyl and aryl may optionally besubstituted with one or more fluorine atoms.

Formula B-1.

Compounds of formula B may include compounds of formula B-1, which arecompounds of formula B wherein j1 is zero and j2 is from 1 to 220, or j2is from 1 to 100, or j2 is from 1 to 50, or j2 is from 1 to 20, or j2 isfrom 1 to 5, or j2 is 1.

B-2.

Compounds of formula B may include compounds of formula B-2, which arecompounds of formula B wherein j1 and j2 are independently from 4 to100, or from 4 to 20, or from 4 to 10, or from 24 to 100, or from 10 to100.

B-3.

Compounds of formulae B, B-1, and B-2 may include compounds of formulaB-3, which are compounds of formula B, B-1, or B-2 wherein R^(A1),R^(A2), R^(A3), and R^(A4) are independently at each occurrence C₁-C₆alkyl or siloxy. Preferred alkyl are C₁-C₃ alkyl, or more preferably,methyl. Preferred siloxy is trimethylsiloxy.

B-4.

Compounds of formulae B, B-1, B-2, and B-3 may include compounds offormula B-4, which are compounds of formula B, B-1, B-2, or B-3 whereinR^(A5) and R^(A7) are independently alkoxy-alkyleneoxy-alkyl, preferablythey are independently a methoxy capped polyethyleneoxyalkyl of formulaCH₃O—[CH₂CH₂O]_(p)—CH₂CH₂CH₂, wherein p is a whole number from 1 to 50.

B-5.

Compounds of formulae B, B-1, B-2, and B-3 may include compounds offormula B-5, which are compounds of formula B, B-1, B-2, or B-3 whereinR^(A5) and R^(A7) are independently siloxy, such as trimethylsiloxy.

B-6.

Compounds of formulae B, B-1, B-2, and B-3 may include compounds offormula B-6, which are compounds of formula B, B-1, B-2, or B-3 whereinR^(A5) and R^(A7) are independently C₁-C₆ alkyl, alternatively C₁-C₄alkyl, or alternatively, butyl or methyl.

B-7.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, and B-6 may includecompounds of formula B-7, which are compounds of formula B, B-1, B-2,B-3, B-4, B-5, or B-6 wherein R^(A6) is C₁-C₈ alkyl, preferably C₁-C₆alkyl, more preferably C₁-C₄ alkyl (for example methyl, ethyl, n-propyl,or n-butyl). More preferably R^(A6) is n-butyl.

B-8.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, and B-7, mayinclude compounds of formula B-8, which are compounds of formula B, B-1,B-2, B-3, B-4, B-5, B-6, or B-7 wherein Rg comprises styryl, vinylcarbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinylamide,(meth)acrylate, or (meth)acrylamide. Preferably, Rg comprises(meth)acrylate, (meth)acrylamide, or styryl. More preferably, Rgcomprises (meth)acrylate or (meth)acrylamide. When Rg is(meth)acrylamide, the nitrogen group may be substituted with R^(A9),wherein R^(A9) is H, C₁-C₈ alkyl (preferably C₁-C₄ alkyl, such asn-butyl, n-propyl, methyl or ethyl), or C₃-C₈ cycloalkyl (preferablyC₅-C₆ cycloalkyl), wherein alkyl and cycloalkyl are optionallysubstituted with one or more groups independently selected fromhydroxyl, amide, ether, silyl (e.g., trimethylsilyl), siloxy (e.g.,trimethylsiloxy), alkyl-siloxanyl (where alkyl is itself optionallysubstituted with fluoro), aryl-siloxanyl (where aryl is itselfoptionally substituted with fluoro), and silyl-oxaalkylene- (where theoxaalkylene is itself optionally substituted with hydroxyl).

B-9.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, and B-8 mayinclude compounds of formula B-9, which are compounds of formula B, B-1,B-2, B-3, B-4, B-5, B-6, B-7, or B-8 wherein the linking group comprisesalkylene (preferably C₁-C₄ alkylene), cycloalkylene (preferably C₅-C₆cycloalkylene), alkyleneoxy (preferably ethyleneoxy), haloalkyleneoxy(preferably haloethyleneoxy), amide, oxaalkylene (preferably containing3 to 6 carbon atoms), siloxanyl, alkylenesiloxanyl, carbamate,alkyleneamine (preferably C₁-C₆ alkyleneamine), or combinations of twoor more thereof, wherein the linking group is optionally substitutedwith one or more substituents independently selected from alkyl,hydroxyl, ether, amine, carbonyl, siloxy, and carbamate.

B-10.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-10, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis alkylene-siloxanyl-alkylene-alkyleneoxy-, oralkylene-siloxanyl-alkylene-[alkyleneoxy-alkylene-siloxanyl]_(q)-alkyleneoxy-,where q is from 1 to 50.

B-11.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-11, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis C₁-C₆ alkylene, preferably C₁-C₃ alkylene, more preferablyn-propylene.

B-12.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-12, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis alkylene-carbamate-oxaalkylene. Preferably, the linking group isCH₂CH₂N(H)—C(═O)—O—CH₂CH₂—O—CH₂CH₂CH₂.

B-13.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-13, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis oxaalkylene. Preferably, the linking group is CH₂CH₂—O—CH₂CH₂CH₂.

B-14.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-14, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis alkylene-[siloxanyl-alkylene]_(q)-, where q is from 1 to 50. Anexample of such a linking group is:—(CH₂)₃—[Si(CH₃)₂—O—Si(CH₃)₂—(CH₂)₂]_(q)—.

B-15.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-15, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis alkyleneoxy-carbamate-alkylene-cycloalkylene-carbamate-oxaalkylene,wherein cycloalkylene is optionally substituted with or 1, 2, or 3independently selected alkyl groups (preferably C₁-C₃ alkyl, morepreferably methyl). An example of such a linking group is—[OCH₂CH₂]_(q)—OC(═O)—NH—CH₂-[1,3-cyclohexylene]-NHC(═O)O—CH₂CH₂—O—CH₂CH₂—,wherein the cyclohexylene is substituted at the 1 and 5 positions with 3methyl groups.

B-16.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-16, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein Rg comprisesstyryl and the linking group is alkyleneoxy wherein each alkylene inalkyleneoxy is independently optionally substituted with hydroxyl. Anexample of such a linking group is —O—(CH₂)₃—. Another example of such alinking group is —O—CH₂CH(OH)CH₂—O—(CH₂)₃—.

B-17.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-17, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein Rg comprisesstyryl and the linking group is alkyleneamine. An example of such alinking group is —NH—(CH₂)₃—.

B-18.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-18, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis oxaalkylene optionally substituted with hydroxyl, siloxy, orsilyl-alkyleneoxy (where the alkyleneoxy is itself optionallysubstituted with hydroxyl). An example of such a linking group is—CH₂CH(G)CH₂—O—(CH₂)₃—, wherein G is hydroxyl. In another example, G isR₃SiO— wherein two R groups are trimethylsiloxy and the third is C₁-C₈alkyl (preferably C₁-C₃ alkyl, more preferably methyl) or the third isC₃-C₈ cycloalkyl. In a further example, G isR₃Si—(CH₂)₃—O—CH₂CH(OH)CH₂—O—, wherein two R groups are trimethylsiloxyand the third is C₁-C₈ alkyl (preferably C₁-C₃ alkyl, more preferablymethyl) or C₃-C₈ cycloalkyl. In a still further example, G is apolymerizable group, such as (meth)acrylate. Such compounds may functionas crosslinkers.

B-19.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-19, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein Rg comprisesstyryl and the linking group is amine-oxaalkylene optionally substitutedwith hydroxyl. An example of such a linking group is—NH—CH₂CH(OH)CH₂—O—(CH₂)₃—.

B-20.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-20, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein Rg comprisesstyryl and the linking group is alkyleneoxy-carbamate-oxaalkylene. Anexample of such a linking group is—O—(CH₂)₂—N(H)C(═O)O—(CH₂)₂—O—(CH₂)₃—.

B-21.

Compounds of formulae B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9may include compounds of formula B-21, which are compounds of formula B,B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 wherein the linking groupis alkylene-carbamate-oxaalkylene. An example of such a linking group is—(CH₂)₂—N(H)C(═O)O—(CH₂)₂—O—(CH₂)₃—.

Formula C.

Silicone-containing components of formulae A, B, B-1, B-2, B-3, B-4,B-5, B-6, B-7, B-8, B-9, B-10, B-11, B-12, B-13, B-14, B-15, B-18, andB-21 may include compounds of formula C, which are compounds of formulaA, B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, B-9, B-10, B-11, B-12,B-13, B-14, B-15, B-18, or B-21 having the structure:

wherein

R^(A8) is hydrogen or methyl;

Z is O, S, or N(R^(A9)); and

L, j1, j2, R^(A1), R^(A2), R^(A3), R^(A4), R^(A5), R^(A6), R^(A7), andR^(A9) are as defined in formula B or its various sub-formulae (e.g.,B-1, B-2, etc.).

C-1.

Compounds of formula C may include (meth)acrylates of formula C-1, whichare compounds of formula C wherein Z is O.

C-2.

Compounds of formula C may include (meth)acrylamides of formula C-2,which are compounds of formula C wherein Z is N(R^(A9)), and R^(A9) isH.

C-3.

Compounds of formulae C may include (meth)acrylamides of formula C-3,which are compounds of formula C wherein Z is N(R^(A9)), and R^(A9) isC₁-C₈ alkyl that is unsubstituted or is optionally substituted asindicated above. Examples of R^(A9) include CH₃, —CH₂CH(OH)CH₂(OH),—(CH₂)₃-siloxanyl, —(CH₂)₃—SiR₃, and —CH₂CH(OH)CH₂—O—(CH₂)₃—SiR₃ whereeach R in the foregoing groups is independently selected fromtrimethylsiloxy, C₁-C₈ alkyl (preferably C₁-C₃ alkyl, more preferablymethyl), and C₃-C₈ cycloalkyl. Further examples of R^(A9) include:—(CH₂)₃—Si(Me)(SiMe₃)₂, and —(CH₂)₃—Si(Me₂)-[O—SiMe₂]₁₋₁₀-CH₃.

Formula D.

Compounds of formula C may include compounds of formula D:

wherein

R^(A8) is hydrogen or methyl;

Z¹ is O or N(R^(A9));

L¹ is alkylene containing 1 to 8 carbon atoms, or oxaalkylene containing3 to 10 carbon atoms, wherein L¹ is optionally substituted withhydroxyl; and

j2, R^(A3), R^(A4), R^(A5), R^(A6), R^(A7), and R^(A9) are as definedabove in formula B or its various sub-formulae (e.g., B-1, B-2, etc.).

D-1.

Compounds of formula D may include compounds of formula D-1, which arecompounds of formula D wherein L¹ is C₂-C₅ alkylene optionallysubstituted with hydroxyl. Preferably L¹ is n-propylene optionallysubstituted with hydroxyl.

D-2.

Compounds of formula D may include compounds of formula D-2, which arecompounds of formula D wherein L¹ is oxaalkylene containing 4 to 8carbon atoms optionally substituted with hydroxyl. Preferably L¹ isoxaalkylene containing five or six carbon atoms optionally substitutedwith hydroxyl. Examples include —(CH₂)₂—O—(CH₂)₃—, and—CH₂CH(OH)CH₂—O—(CH₂)₃—.

D-3.

Compounds of formulae D, D-1, and D-2 may include compounds of formulaD-3, which are compounds of formula D, D-1, or D-2 wherein Z¹ is O.

D-4.

Compounds of formulae D, D-1, and D-2 may include compounds of formulaD-4, which are compounds of formula D, D-1, or D-2 wherein Z¹ isN(R^(A9)), and R^(A9) is H.

D-5.

Compounds of formulae D, D-1, and D-2 may include compounds of formulaD-5, which are compounds of formula D, D-1, or D-2 wherein Z¹ isN(R^(A9)), and R^(A9) is C₁-C₄ alkyl optionally substituted with 1 or 2substituents selected from hydroxyl, siloxy, and C₁-C₆ alkyl-siloxanyl-.

D-6.

Compounds of formulae D, D-1, D-2, D-3, D-4, and D-5 may includecompounds of formula D-6, which are compounds of formula D, D-1, D-2,D-3, D-4, or D-5 wherein j2 is 1.

D-7.

Compounds of formulae D, D-1, D-2, D-3, D-4, and D-5 may includecompounds of formula D-7, which are compounds of formula D, D-1, D-2,D-3, D-4, or D-5 wherein j2 is from 2 to 220, or from 2 to 100, or from10 to 100, or from 24 to 100, or from 4 to 20, or from 4 to 10.

D-8.

Compounds of formulae D, D-1, D-2, D-3, D-4, D-5, D-6, and D-7 mayinclude compounds of formula D-8, which are compounds of formula D, D-1,D-2, D-3, D-4, D-5, D-6, or D-7 wherein R^(A3), R^(A4), R^(A5), R^(A6),and R^(A7) are independently C₁-C₆ alkyl or siloxy. Preferably R^(A3),R^(A4), R^(A5), R^(A6), and R^(A7) are independently selected frommethyl, ethyl, n-propyl, n-butyl, and trimethylsiloxy. More preferably,R^(A3), R^(A4), R^(A5), R^(A6), and R^(A7) are independently selectedfrom methyl, n-butyl, and trimethylsiloxy.

D-9.

Compounds of formulae D, D-1, D-2, D-3, D-4, D-5, D-6, and D-7 mayinclude compounds of formula D-9, which are compounds of formula D, D-1,D-2, D-3, D-4, D-5, D-6, or D-7 wherein R^(A3) and R^(A4) areindependently C₁-C₆ alkyl (e.g., methyl or ethyl) or siloxy (e.g.,trimethylsiloxy), and R^(A5), R^(A6), and R^(A7) are independently C₁-C₆alkyl (e.g., methyl, ethyl, n-propyl, or n-butyl).

Formula E.

The silicone-containing component for use in the invention may comprisea multi-functional silicone-containing component. Thus, for example, thesilicone-containing component of formula A may comprise a bifunctionalmaterial of formula E:

wherein

Rg, L, j1, j2, R^(A1), R^(A2), R^(A3), R^(A4), R^(A5), and R^(A7) are asdefined above for formula B or its various sub-formulae (e.g., B-1, B-2,etc.);

L² is a linking group; and

Rg¹ is a polymerizable group.

E-1.

Compounds of formula E may include compounds of formula E-1, which arecompounds of formula E wherein Rg and Rg¹ are each a vinyl carbonate ofstructure CH₂═CH—O—C(═O)—O— or structure CH₂═C(CH₃)—O—C(═O)—O—.

E-2.

Compounds of formula E may include compounds of formula E-2, which arecompounds of formula E wherein Rg and Rg¹ are each (meth)acrylate.

E-3.

Compounds of formula E may include compounds of formula E-3, which arecompounds of formula E wherein Rg and Rg¹ are each (meth)acrylamide,wherein the nitrogen group may be substituted with R^(A9) (whereinR^(A9) is as defined above).

E-4.

Suitable compounds of formulae E, E-1, E-2, and E-3 include compounds offormula E-4, which are compounds of formula E, E-1, E-2, or E-3 whereinj1 is zero and j2 is from 1 to 220, or j2 is from 1 to 100, or j2 isfrom 1 to 50, or j2 is from 1 to 20.

E-5.

Suitable compounds of formulae E, E-1, E-2, and E-3 include compounds offormula E-5, which are compounds of formula E, E-1, E-2, or E-3, whereinj1 and j2 are independently from 4 to 100.

E-6.

Suitable compounds of formulae E, E-1, E-2, E-3, E-4, and E-5 includecompounds of formula E-6, which are compounds of formula E, E-1, E-2,E-3, E-4, or E-5 wherein R^(A1), R^(A2), R^(A3), R^(A4), and R^(A5) areindependently at each occurrence C₁-C₆ alkyl, preferably they areindependently C₁-C₃ alkyl, or preferably, each is methyl.

E-7.

Suitable compounds of formulae E, E-1, E-2, E-3, E-4, E-5, and E-6include compounds of formula E-7, which are compounds of formula E, E-1,E-2, E-3, E-4, E-5, or E-6 wherein R^(A7) is alkoxy-alkyleneoxy-alkyl,preferably it is a methoxy capped polyethyleneoxyalkyl of formulaCH₃O—[CH₂CH₂O]_(p)—CH₂CH₂CH₂, wherein p is a whole number from 1 to 50,or from 1 to 30, or from 1 to 10, or from 6 to 10.

E-8.

Suitable compounds of formulae E, E-1, E-2, E-3, E-4, E-5, E-6, and E-7include compounds of formula E-8, which are compounds of formula E, E-1,E-2, E-3, E-4, E-5, E-6, or E-7 wherein L comprises alkylene, carbamate,siloxanyl, cycloalkylene, amide, haloalkyleneoxy, oxaalkylene, orcombinations of two or more thereof, wherein the linking group isoptionally substituted with one or more substituents independentlyselected from alkyl, hydroxyl, ether, amine, carbonyl, and carbamate.

E-9.

Suitable compounds of formulae E, E-1, E-2, E-3, E-4, E-5, E-6, E-7, andE-8 include compounds of formula E-9, which are compounds of formula E,E-1, E-2, E-3, E-4, E-5, E-6, E-7, or E-8 wherein L² comprises alkylene,carbamate, siloxanyl, cycloalkylene, amide, haloalkyleneoxy,oxaalkylene, or combinations of two or more thereof, wherein the linkinggroup is optionally substituted with one or more substituentsindependently selected from alkyl, hydroxyl, ether, amine, carbonyl, andcarbamate.

Examples of silicone-containing components suitable for use in theinvention include, but are not limited to, compounds listed in Table 3.Where the compounds in Table 3 contain polysiloxane groups, the numberof SiO repeat units in such compounds, unless otherwise indicated, ispreferably from 3 to 100, more preferably from 3 to 40, or still morepreferably from 3 to 20.

TABLE 3 1 mono-methacryloxypropyl terminated mono-n-butyl terminatedpolydimethylsiloxanes (mPDMS) (preferably containing from 3 to 15 SiOrepeating units) 2 mono-acryloxypropyl terminated mono-n-butylterminated polydimethylsiloxane 3 mono(meth)acryloxypropyl terminatedmono-n-methyl terminated polydimethylsiloxane 4 mono(meth)acryloxypropylterminated mono-n-butyl terminated polydiethylsiloxane 5mono(meth)acryloxypropyl terminated mono-n-methyl terminatedpolydiethylsiloxane 6 mono(meth)acrylamidoalkylpolydialkylsiloxanes 7mono(meth)acryloxyalkyl terminated mono-alkyl polydiarylsiloxanes 83-methacryloxypropyltris(trimethylsiloxy)silane (TRIS) 93-methacryloxypropylbis(trimethylsiloxy)methylsilane 103-methacryloxypropylpentamethyl disiloxane 11mono(meth)acrylamidoalkylpolydialkylsiloxanes 12mono(meth)acrylamidoalkyl polydimethylsiloxanes 13N-(2,3-dihydroxypropane)-N′-(propyl tetra(dimethylsiloxy)dimethylbutylsilane)acrylamide 14N-[3-tris(trimethylsiloxy)silyl]-propyl acrylamide (TRIS-Am) 152-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propylmethacrylate (SiMAA) 162-hydroxy-3-methacryloxypropyloxypropyl-tris(trimethylsiloxy)silane 17mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminatedmono-n-butyl terminated polydimethylsiloxanes (OH-mPDMS) (containingfrom 4 to 30, or from 10 to 20, or from 4 to 8 SiO repeat units) 18

19

20

21

22

23

24

Additional non-limiting examples of suitable silicone-containingcomponents are listed in Table 4. Unless otherwise indicated, j2 whereapplicable is preferably from 1 to 100, more preferably from 3 to 40, orstill more preferably from 3 to 15. In compounds containing j1 and j2,the sum of j1 and j2 is preferably from 2 to 100, more preferably from 3to 40, or still more preferably from 3 to 15.

TABLE 4 25

26

27

28

29

30 1,3-bis[4-(vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane 313-(vinyloxycarbonylthio) propyl-[tris (trimethylsiloxy)silane] 323-[tris(trimethylsiloxy)silyl] propyl allyl carbamate 333-[tris(trimethylsiloxy)silyl] propyl vinyl carbamate 34tris(trimethylsiloxy)silylstyrene (Styryl-TRIS) 35

36

37

38

39

40

41

Silicone-containing components for use in the invention may have anaverage molecular weight of from about 400 to about 4000 daltons.

The silicone containing component(s) may be present in amounts up toabout 95 weight %, or from about 10 to about 80 weight %, or from about20 to about 70 weight %, based upon all reactive components of thereactive mixture (excluding diluents).

Polyamides

The reactive monomer mixture may include at least one polyamide. As usedherein, the term “polyamide” refers to polymers and copolymerscomprising repeating units containing amide groups. The polyamide maycomprise cyclic amide groups, acyclic amide groups and combinationsthereof and may be any polyamide known to those of skill in the art.Acyclic polyamides comprise pendant acyclic amide groups and are capableof association with hydroxyl groups. Cyclic polyamides comprise cyclicamide groups and are capable of association with hydroxyl groups.

Examples of suitable acyclic polyamides include polymers and copolymerscomprising repeating units of Formulae G1 and G2:

wherein X is a direct bond, —(CO)—, or —(CONHR₄₄)—, wherein R₄₄ is a C₁to C₃ alkyl group; R₄₀ is selected from H, straight or branched,substituted or unsubstituted C₁ to C₄ alkyl groups; R₄₁ is selected fromH, straight or branched, substituted or unsubstituted C₁ to C₄ alkylgroups, amino groups having up to two carbon atoms, amide groups havingup to four carbon atoms, and alkoxy groups having up to two carbongroups; R₄₂ is selected from H, straight or branched, substituted orunsubstituted C₁ to C₄ alkyl groups; or methyl, ethoxy, hydroxyethyl,and hydroxymethyl; R₄₃ is selected from H, straight or branched,substituted or unsubstituted C₁ to C₄ alkyl groups; or methyl, ethoxy,hydroxyethyl, and hydroxymethyl; wherein the number of carbon atoms inR₄₀ and R₄₁ taken together is 8 or less, including 7, 6, 5, 4, 3, orless; and wherein the number of carbon atoms in R₄₂ and R₄₃ takentogether is 8 or less, including 7, 6, 5, 4, 3, or less. The number ofcarbon atoms in R₄₀ and R₄₁ taken together may be 6 or less or 4 orless. The number of carbon atoms in R₄₂ and R₄₃ taken together may be 6or less. As used herein substituted alkyl groups include alkyl groupssubstituted with an amine, amide, ether, hydroxyl, carbonyl or carboxygroups or combinations thereof.

R₄₀ and R₄₁ may be independently selected from H, substituted orunsubstituted C₁ to C₂ alkyl groups. X may be a direct bond, and R₄₀ andR₄₁ may be independently selected from H, substituted or unsubstitutedC₁ to C₂ alkyl groups. R₄₂ and R₄₃ can be independently selected from H,substituted or unsubstituted C₁ to C₂ alkyl groups, methyl, ethoxy,hydroxyethyl, and hydroxymethyl.

The acyclic polyamides of the present invention may comprise a majorityof the repeating units of Formula LV or Formula LVI, or the acyclicpolyamides can comprise at least 50 mole percent of the repeating unitof Formula G or Formula G1, including at least 70 mole percent, and atleast 80 mole percent. Specific examples of repeating units of Formula Gand Formula G1 include repeating units derived fromN-vinyl-N-methylacetamide, N-vinylacetamide,N-vinyl-N-methylpropionamide, N-vinyl-N-methyl-2-methylpropionamide,N-vinyl-2-methyl-propionamide, N-vinyl-N,N′-dimethylurea, N,N-dimethylacrylamide, methacrylamide, and acyclic amides of Formulae G2and G3:

Examples of suitable cyclic amides that can be used to form the cyclicpolyamides of include α-lactam, β-lactam, γ-lactam, δ-lactam, andε-lactam. Examples of suitable cyclic polyamides include polymers andcopolymers comprising repeating units of Formula G4:

wherein R₄₅ is a hydrogen atom or methyl group; wherein f is a numberfrom 1 to 10; wherein X is a direct bond, —(CO)—, or —(CONHR₄₆)—,wherein R₄₆ is a C₁ to C₃ alkyl group. In Formula LIX, f may be 8 orless, including 7, 6, 5, 4, 3, 2, or 1. In Formula G4, f may be 6 orless, including 5, 4, 3, 2, or 1. In Formula G4, f may be from 2 to 8,including 2, 3, 4, 5, 6, 7, or 8. In Formula LIX, f may be 2 or 3. WhenX is a direct bond, f may be 2. In such instances, the cyclic polyamidemay be polyvinylpyrrolidone (PVP).

The cyclic polyamides of the present invention may comprise 50 molepercent or more of the repeating unit of Formula G4, or the cyclicpolyamides can comprise at least 50 mole percent of the repeating unitof Formula G4, including at least 70 mole percent, and at least 80 molepercent.

The polyamides may also be copolymers comprising repeating units of bothcyclic and acyclic amides. Additional repeating units may be formed frommonomers selected from hydroxyalkyl(meth)acrylates,alkyl(meth)acrylates, other hydrophilic monomers and siloxanesubstituted (meth)acrylates. Any of the monomers listed as suitablehydrophilic monomers may be used as comonomers to form the additionalrepeating units. Specific examples of additional monomers which may beused to form polyamides include 2-hydroxyethyl (meth)acrylate, vinylacetate, acrylonitrile, hydroxypropyl (meth)acrylate, methyl(meth)acrylate and hydroxybutyl (meth)acrylate, dihydroxypropyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, and the like andmixtures thereof. Ionic monomers may also be included. Examples of ionicmonomers include (meth)acrylic acid, N-[(ethenyloxy)carbonyl]-β-alanine(VINAL, CAS #148969-96-4), 3-acrylamidopropanoic acid (ACA1),5-acrylamidopentanoic acid (ACA2), 3-acrylamido-3-methylbutanoic acid(AMBA), 2-(methacryloyloxy)ethyl trimethylammonium chloride (Q Salt orMETAC), 2-acrylamido-2-methylpropane sulfonic acid (AMPS),1-propanaminium,N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-, innersalt (CBT, carboxybetaine; CAS 79704-35-1), 1-propanaminium,N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-, innersalt (SBT, sulfobetaine, CAS 80293-60-3),3,5-Dioxa-8-aza-4-phosphaundec-10-en-1-aminium,4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide (9CI) (PBT,phosphobetaine, CAS 163674-35-9, 2-methacryloyloxyethylphosphorylcholine, 3-(dimethyl(4-vinylbenzyl)ammonio)propane-1-sulfonate(DMVBAPS), 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate(AMPDAPS),3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate(MAMPDAPS),3-((3-(acryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (APDAPS),methacryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (MAPDAPS).

The reactive monomer mixture may comprise both an acyclic polyamide anda cyclic polyamide or copolymers thereof. The acyclic polyamide can beany of those acyclic polyamides described herein or copolymers thereof,and the cyclic polyamide can be any of those cyclic polyamides describedherein or copolymers thereof. The polyamide may be selected from thegroup polyvinylpyrrolidone (PVP), polyvinylmethyacetamide (PVMA),polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA),poly(hydroxyethyl(meth)acrylamide), polyacrylamide, and copolymers andmixtures thereof.

The total amount of all polyamides in the reactive mixture may be in therange of between 1 weight percent and about 35 weight percent, includingin the range of about 1 weight percent to about 15 weight percent, andin the range of about 5 weight percent to about 15 weight percent, inall cases, based on the total weight of the reactive components of thereactive monomer mixture.

Without intending to be bound by theory, when used with a siliconehydrogel, the polyamide functions as an internal wetting agent. Thepolyamides of the present invention may be non-polymerizable, and inthis case, are incorporated into the silicone hydrogels assemi-interpenetrating networks. The polyamides are entrapped orphysically retained within the silicone hydrogels. Alternatively, thepolyamides of the present invention may be polymerizable, for example aspolyamide macromers or prepolymers, and in this case, are covalentlyincorporated into the silicone hydrogels. Mixtures of polymerizable andnon-polymerizable polyamides may also be used.

When the polyamides are incorporated into the reactive monomer mixturethey may have a weight average molecular weight of at least 100,000daltons; greater than about 150,000; between about 150,000 to about2,000,000 daltons; between about 300,000 to about 1,800,000 daltons.Higher molecular weight polyamides may be used if they are compatiblewith the reactive monomer mixture.

Cross-Linking Agents

It is generally desirable to add one or more cross-linking agents, alsoreferred to as cross-linking monomers, multi-functional macromers, andprepolymers, to the reactive mixture. The cross-linking agents may beselected from bifunctional crosslinkers, trifunctional crosslinkers,tetrafunctional crosslinkers, and mixtures thereof, includingsilicone-containing and non-silicone containing cross-linking agents.Non-silicone-containing cross-linking agents include ethylene glycoldimethacrylate (EGDMA), tetraethylene glycol dimethacrylate (TEGDMA),trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC),glycerol trimethacrylate, methacryloxyethyl vinylcarbonate (HEMAVc),allylmethacrylate, methylene bisacrylamide (MBA), and polyethyleneglycol dimethacrylate wherein the polyethylene glycol has a molecularweight up to about 5000 Daltons. The cross-linking agents are used inthe usual amounts, e.g., from about 0.000415 to about 0.0156 mole per100 grams of reactive Formulas in the reactive mixture. Alternatively,if the hydrophilic monomers and/or the silicone-containing componentsare multifunctional by molecular design or because of impurities, theaddition of a cross-linking agent to the reactive mixture is optional.Examples of hydrophilic monomers and macromers which can act as thecross-linking agents and when present do not require the addition of anadditional cross-linking agent to the reactive mixture include(meth)acrylate and (meth)acrylamide endcapped polyethers. Othercross-linking agents will be known to one skilled in the art and may beused to make the silicone hydrogel of the present invention.

It may be desirable to select crosslinking agents with similarreactivity to one or more of the other reactive components in theformulation. In some cases, it may be desirable to select a mixture ofcrosslinking agents with different reactivity in order to control somephysical, mechanical or biological property of the resulting siliconehydrogel. The structure and morphology of the silicone hydrogel may alsobe influenced by the diluent(s) and cure conditions used.

Multifunctional silicone-containing components, including macromers,cross-linking agents, and prepolymers, may also be included to furtherincrease the modulus and retain tensile strength. The siliconecontaining cross-linking agents may be used alone or in combination withother cross-linking agents. An example of a silicone containingcomponent which can act as a cross-linking agent and, when present, doesnot require the addition of a crosslinking monomer to the reactivemixture includes α, ω-bismethacryloxypropyl polydimethylsiloxane.

Cross-linking agents that have rigid chemical structures andpolymerizable groups that undergo free radical polymerization may alsobe used. Non-limiting examples of suitable rigid structures includecross-linking agents comprising phenyl and benzyl ring, such are1,4-phenylene diacrylate, 1,4-phenylene dimethacrylate,2,2-bis(4-methacryloxyphenyl)-propane,2,2-bis[4-(2-acryloxyethoxy)phenyl]propane,2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)-phenyl]propane, and4-vinylbenzyl methacrylate, and combinations thereof. Rigid crosslinkingagents may be included in amounts between about 0.5 and about 15, or2-10, 3-7 based upon the total weight of all of the reactive components.The physical and mechanical properties of the silicone hydrogels of thepresent invention may be optimized for a particular use by adjusting thecomponents in the reactive mixture.

Non-limiting examples of silicone cross-linking agents also include themulti-functional silicone-containing components described above, such ascompounds of Formula E (and its sub-formulae) and the multi-functionalcompounds shown in Table 3.

Further Constituents

The reactive monomer mixture may contain additional components such as,but not limited to, diluents, initiators, UV absorbers, visible lightabsorbers, photochromic compounds, pharmaceuticals, nutraceuticals,antimicrobial substances, tints, pigments, copolymerizable dyes,nonpolymerizable dyes, release agents, and combinations thereof.

Classes of suitable diluents for silicone hydrogel reactive mixturesinclude alcohols having 2 to 20 carbon atoms, amides having 10 to 20carbon atoms derived from primary amines and carboxylic acids having 8to 20 carbon atoms. The diluents may be primary, secondary, and tertiaryalcohols.

Generally, the reactive components are mixed in a diluent to form areactive mixture. Suitable diluents are known in the art. For siliconehydrogels, suitable diluents are disclosed in WO 03/022321 and U.S. Pat.No. 6,020,445, the disclosure of which is incorporated herein byreference. Classes of suitable diluents for silicone hydrogel reactivemixtures include alcohols having 2 to 20 carbons, amides having 10 to 20carbon atoms derived from primary amines, and carboxylic acids having 8to 20 carbon atoms. Primary and tertiary alcohols may be used. Preferredclasses include alcohols having 5 to 20 carbons and carboxylic acidshaving 10 to 20 carbon atoms. Specific diluents which may be usedinclude 1-ethoxy-2-propanol, diisopropylaminoethanol, isopropanol,3,7-dimethyl-3-octanol, 1-decanol, 1-dodecanol, 1-octanol, 1-pentanol,2-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol,tert-amyl alcohol, tert-butanol, 2-butanol, 1-butanol,2-methyl-2-pentanol, 2-propanol, 1-propanol, ethanol, 2-ethyl-1-butanol,(3-acetoxy-2-hydroxypropyloxy)-propylbis(trimethylsiloxy) methylsilane,1-tert-butoxy-2-propanol, 3,3-dimethyl-2-butanol, tert-butoxyethanol,2-octyl-1-dodecanol, decanoic acid, octanoic acid, dodecanoic acid,2-(diisopropylamino)ethanol mixtures thereof and the like. Examples ofamide diluents include N,N-dimethyl propionamide and dimethyl acetamide.

Preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol,1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol,3-methyl-3-pentanol, 2-pentanol, t-amyl alcohol, tert-butanol,2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, ethanol,3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, decanoic acid, octanoicacid, dodecanoic acid, mixtures thereof and the like.

More preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol,1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol,1-dodecanol, 3-methyl-3-pentanol, 1-pentanol, 2-pentanol, t-amylalcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol,2-ethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, mixturesthereof and the like. If a diluent is present, generally there are noparticular restrictions with respect to the amount of diluent present.When diluent is used, the diluent may be present in an amount in therange of about 2 to about 70 weight percent, including in the range ofabout 5 to about 50 weight percent, and in the range of about 15 toabout 40 weight percent, based on the total weight of the reactivemixtures (including reactive and nonreactive Formulas). Mixtures ofdiluents may be used.

A polymerization initiator may be used in the reactive mixture. Thepolymerization initiator may include, for instance, at least one oflauroyl peroxide, benzoyl peroxide, iso-propyl percarbonate,azobisisobutyronitrile, and the like, that generate free radicals atmoderately elevated temperatures, and photoinitiator systems such asaromatic alpha-hydroxy ketones, alkoxyoxybenzoins, acetophenones,acylphosphine oxides, bisacylphosphine oxides, and a tertiary amine plusa diketone, mixtures thereof and the like. Illustrative examples ofphotoinitiators are 1-hydroxycyclohexyl phenyl ketone,2-hydroxy-2-methyl-1-phenyl-propan-1-one,bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide(DMBAPO), bis(2,4,6-trimethylbenzoyl)-phenyl phosphine eoxide (Irgacure819), 2,4,6-trimethylbenzyldiphenyl phosphine oxide and2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzoin methyl ester anda combination of cam-phorquinone and ethyl4-(N,N-dimethylamino)benzoate.

Commercially available visible light initiator systems include Irgacure®819, Irgacure® 1700, Irgacure® 1800, Irgacure® 819, Irgacure® 1850 (allfrom Ciba Specialty Chemicals) and Lucrin® TPO initiator (available fromBASF). Commercially available UV photoinitiators include Darocur® 1173and Darocur® 2959 (Ciba Specialty Chemicals). These and otherphotoinitiators which may be used are disclosed in Volume III,Photoinitiators for Free Radical Cationic & Anionic Photopolymerization,2nd Edition by J. V. Crivello & K. Dietliker; edited by G. Bradley; JohnWiley and Sons; New York; 1998. The initiator is used in the reactivemixture in effective amounts to initiate photopolymerization of thereactive mixture, e.g., from about 0.1 to about 2 parts by weight per100 parts of reactive monomer mixture. Polymerization of the reactivemixture can be initiated using the appropriate choice of heat or visibleor ultraviolet light or other means depending on the polymerizationinitiator used. Alternatively, initiation can be conducted using e-beamwithout a photoinitiator. However, when a photoinitiator is used, thepreferred initiators are bisacylphosphine oxides, such asbis(2,4,6-tri-methylbenzoyl)-phenyl phosphine oxide (Irgacure® 819) or acombination of 1-hydroxycyclohexyl phenyl ketone andbis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide(DMBAPO).

The reactive mixture for making the ophthalmic devices of the inventionmay comprise, in addition to a hydroxybiphenyl benzotriazole of formulaI, any of the polymerizable compounds and optional components describedabove.

Preferred reactive mixtures may comprise: a hydroxybiphenylbenzotriazole of formula I and a hydrophilic monomer.

Preferred reactive mixtures may comprise: a hydroxybiphenylbenzotriazole of formula I; and a hydrophilic monomer selected from DMA,NVP, HEMA, VMA, NVA, methacrylic acid, and mixtures thereof. Preferredare mixtures of HEMA and methacrylic acid.

Preferred reactive mixtures may comprise: a hydroxybiphenylbenzotriazole of formula I, a hydrophilic monomer, and asilicone-containing component.

Preferred reactive mixtures may comprise: a hydroxybiphenylbenzotriazole of formula I, a hydrophilic monomer, and asilicone-containing component comprising a compound of formula D (or itssub-formulae, such as D-1, D-2, etc.).

Preferred reactive mixtures may comprise: a hydroxybiphenylbenzotriazole of formula I, a hydrophilic monomer selected from DMA,NVP, HEMA, VMA, NVA, and mixtures thereof; a silicone-containingcomponent comprising a compound of formula D (or its sub-formulae, suchas D-1, D-2, etc.); and an internal wetting agent.

Preferred reactive mixtures may comprise: a hydroxybiphenylbenzotriazole of formula I, a hydrophilic monomer selected from DMA,HEMA and mixtures thereof; a silicone-containing component selected from2-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propylmethacrylate (SiMAA), mono-methacryloxypropyl terminated mono-n-butylterminated polydimethylsiloxane (mPDMS),mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminatedmono-n-butyl terminated polydimethylsiloxane (OH-mPDMS), and mixturesthereof; and a wetting agent (preferably PVP or PVMA). For thehydrophilic monomer, mixtures of DMA and HEMA are preferred. For thesilicone containing component, mixtures of SiMAA and mPDMS arepreferred.

The foregoing reactive mixtures may contain optional ingredients suchas, but not limited to, one or more initiators, internal wetting agents,crosslinkers, other UV blockers, and diluents.

Curing of Hydrogels and Manufacture of Lens

The reactive mixtures may be formed by any of the methods known in theart, such as shaking or stirring, and used to form polymeric articles ordevices by known methods. The reactive components are mixed togethereither with or without a diluent to form the reactive mixture.

For example, hydrogels may be prepared by mixing reactive components,and, optionally, diluent(s), with a polymerization initiator and curingby appropriate conditions to form a product that can be subsequentlyformed into the appropriate shape by lathing, cutting, and the like.Alternatively, the reactive mixture may be placed in a mold andsubsequently cured into the appropriate article.

A method of making a silicone hydrogel contact lens may comprise:preparing a reactive monomer mixture; transferring the reactive monomermixture onto a first mold; placing a second mold on top the first moldfilled with the reactive monomer mixture; and curing the reactivemonomer mixture by free radical copolymerization to form the siliconehydrogel in the shape of a contact lens.

The reactive mixture may be cured via any known process for molding thereactive mixture in the production of contact lenses, includingspincasting and static casting. Spincasting methods are disclosed inU.S. Pat. Nos. 3,408,429 and 3,660,545, and static casting methods aredisclosed in U.S. Pat. Nos. 4,113,224 and 4,197,266. The contact lensesof this invention may be formed by the direct molding of the siliconehydrogels, which is economical, and enables precise control over thefinal shape of the hydrated lens. For this method, the reactive mixtureis placed in a mold having the shape of the final desired siliconehydrogel and the reactive mixture is subjected to conditions whereby themonomers polymerize, thereby producing a polymer in the approximateshape of the final desired product.

After curing, the lens may be subjected to extraction to removeunreacted components and release the lens from the lens mold. Theextraction may be done using conventional extraction fluids, suchorganic solvents, such as alcohols or may be extracted using aqueoussolutions.

Aqueous solutions are solutions which comprise water. The aqueoussolutions of the present invention may comprise at least about 20 weightpercent water, or at least about 50 weight percent water, or at leastabout 70 weight percent water, or at least about 95 weight percentwater. Aqueous solutions may also include additional water solubleFormulas such as inorganic salts or release agents, wetting agents, slipagents, pharmaceutical and nutraceutical Formulas, combinations thereofand the like. Release agents are compounds or mixtures of compoundswhich, when combined with water, decrease the time required to release acontact lens from a mold, as compared to the time required to releasesuch a lens using an aqueous solution that does not comprise the releaseagent. The aqueous solutions may not require special handling, such aspurification, recycling or special disposal procedures.

Extraction may be accomplished, for example, via immersion of the lensin an aqueous solution or exposing the lens to a flow of an aqueoussolution. Extraction may also include, for example, one or more of:heating the aqueous solution; stirring the aqueous solution; increasingthe level of release aid in the aqueous solution to a level sufficientto cause release of the lens; mechanical or ultrasonic agitation of thelens; and incorporating at least one leaching or extraction aid in theaqueous solution to a level sufficient to facilitate adequate removal ofunreacted components from the lens. The foregoing may be conducted inbatch or continuous processes, with or without the addition of heat,agitation or both.

Application of physical agitation may be desired to facilitate leach andrelease. For example, the lens mold part to which a lens is adhered canbe vibrated or caused to move back and forth within an aqueous solution.Other methods may include ultrasonic waves through the aqueous solution.

The lenses may be sterilized by known means such as, but not limited to,autoclaving.

The hydroxybiphenyl benzotriazole compositions of the invention mayabsorb UV radiation over a wavelength range comprising 200-370 nm,preferably comprising 200-380 nm, while transmitting wavelengths longerthan about 400 nm or longer than about 425 nm. Within the 200-370 nm or200-380 nm ranges, the hydroxybiphenyl benzotriazole compositions, whenincorporated in a hydrogel lens, may block 70%, 80%, 85%, 90%, or 95% ofthe radiation. For instance, in a UV transmittance spectrum of aconventional or silicone hydrogel lens containing the hydroxybiphenylbenzotriazole composition of the invention at a concentration of about0.6 mol % and having a center thickness of at least about 88 microns,the maximum transmittance of radiation within the indicated wavelengthrange may be up to 30%, alternatively up to 20%, alternatively up to15%, alternatively up to 10% or alternatively up to 5%. Exemplaryprocedures for measuring transmittance are described below.

Silicone hydrogel ophthalmic devices (e.g., contact lenses) according tothe invention preferably have the following properties. All values areprefaced by “about,” and the devices may have any combination of thelisted properties. The properties may be determined by methods known tothose skilled in the art, for instance as described in United Statespre-grant publication US20180037690, which is incorporated herein byreference.

[H₂O] %: at least 20%, or at least 25%

Haze: 30% or less, or 10% or less

Kruss DCA (°): 100° or less, or 50° or less

Tensile Modulus (psi): 120 or less, or 80 to 120

Dk (barrers): at least 80, or at least 100, or at least 150, or at least200

Elongation to Break: at least 100

For ionic silicon hydrogels, the following properties may also bepreferred (in addition to those recited above):

Lysozyme uptake (μg/lens): at least 100, or at least 150, or at least500, or at least 700

Polyquaternium 1 (PQ1) uptake (%): 15 or less, or 10 or less, or 5 orless

Some embodiments of the invention will now be described in detail in thefollowing Examples.

UV-VIS Test Methods

Ultraviolet-visible spectra of organic compounds in solution weremeasured on a Perkin Elmer Lambda 45 or an Agilent Cary 6000i UV/VISscanning spectrometer. The instrument was thermally equilibrated for atleast thirty minutes prior to use. For the Perkin Elmer instrument, thescan range was 200-800 nm; the scan speed was 960 nm per minute; theslit width was 4 nm; the mode was set on transmission or absorbance; andbaseline correction was selected. For the Cary instrument, the scanrange was 200-800 nm; the scan speed was 600 nm/min; the slit width was2 nm; the mode was transmission or absorbance; and baseline correctionwas selected. A baseline correction was performed before samples wereanalyzed using the autozero function.

Ultraviolet-visible spectra of contact lenses were measured on a PerkinElmer Lambda 45 UV/VIS or an Agilent Cary 6000i UV/VIS scanningspectrometer using packing solution. The instrument was thermallyequilibrated for at least thirty minutes prior to use. For the PerkinElmer instrument, the scan range was 200-800 nm; the scan speed was 960nm per minute; the slit width was 4 nm; the mode was set ontransmission; and baseline correction was selected. Baseline correctionwas performed using cuvettes containing plastic two-piece lens holdersand the same solvents. These two-piece contact lens holders weredesigned to hold the sample in the quartz cuvette in the locationthrough which the incident light beam traverses. The reference cuvettealso contained a two-piece holder. To ensure that the thickness of thesamples is constant, all lenses were made using identical molds. Thecenter thickness of the contact lens was measured using an electronicthickness gauge. Reported center thickness and percent transmissionspectra are obtained by averaging three individual lens data.

It is important to ensure that the outside surfaces of the cuvette arecompletely clean and dry and that no air bubbles are present in thecuvette. Repeatability of the measurement is improved when the referencecuvette and its lens holder remain constant and when all samples use thesame sample cuvette and its lens holder, making sure that both cuvettesare properly inserted into the instrument.

EXAMPLES

The following abbreviations will be used throughout the Examples andFigures and have the following meanings:

BC: back curve plastic mold

FC: front curve plastic mold

Da: dalton or g/mole

kDa: kilodalton or an atomic mass unit equal to 1,000 daltons

DMA: N, N-dimethylacrylamide (Jarchem)

HEMA: 2-hydroxyethyl methacrylate (Bimax)

PVP: poly(N-vinylpyrrolidone) (ISP Ashland)

TEGDMA: tetraethylene glycol dimethacrylate (Esstech)

Irgacure 184: 1-hydroxy-cyclohexyl-phenyl ketone

Irgacure 819: bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (BASF orCiba Specialty Chemicals)

Irgacure 1870: blend ofbis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphineoxide and1-hydroxy-cyclohexyl-phenyl-ketone (BASF or Ciba Specialty Chemicals)

mPDMS: mono-n-butyl terminated monomethacryloxypropyl terminatedpolydimethylsiloxane (M_(n)=800-1000 daltons) (Gelest)

HO-mPDMS: mono-n-butyl terminatedmono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminatedpolydimethylsiloxane (M_(n)=400-1500 daltons) (Ortec or DSM-PolymerTechnology Group)

SiMAA: 2-propenoic acid,2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propylester (Toray) or3-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propoxy)-2-hydroxypropylmethacrylate

D3O: 3,7-dimethyl-3-octanol (Vigon)

DI water: deionized water

MeOH: methanol

IPA: isopropyl alcohol

TFA: trifluoroacetic acid

EDC: ethyl dimethylaminopropyl carbodiimide hydrochloride

DIPCDI: diisopropyl carbodiimide

DMAP: N,N-dimethylaminopyridine

B₂(pin)₂: 1,1′-bis(diphenylphosphino)ferrocene dichloropalladium(II)

Norbloc: 2-(2′-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole(Janssen)

PP: polypropylene which is the homopolymer of propylene

TT: Tuftec which is a hydrogenated styrene butadiene block copolymer(Asahi Kasei Chemicals)

Z: Zeonor which is a polycycloolefin thermoplastic polymer (Nippon ZeonCo Ltd) TL03 lights: Phillips TLK 40W/03 bulbs

Borate Buffered Packing Solution: 18.52 grams (300 mmol) of boric acid,3.7 grams (9.7 mmol) of sodium borate decahydrate, and 28 grams (197mmol) of sodium sulfate were dissolved in enough deionized water to filla 2 liter volumetric flask.

Example 1—Synthesis of Compound (D) as Shown in Scheme 2

3-(3-(2H-Benzo[d][1,2,3]triazol-2-yl)-5-bromo-4-hydroxyphenyl)propanoicacid (B)

Bromine (4.18 mL, 81 mmol, 1.1 eq.) was added dropwise to a solution ofcompound (A) (25 g, 74 mmol, 1 eq.) in trifluoroacetic acid (750 mL).The reaction was heated to 65° C. for 3 hours. Additional bromine (1.9mL, 37.0 mmol, 0.5 eq.) was added and the reaction was heated to 75° C.for 2.5 hours. The mixture consisting of a mixture of components wasallowed to cool to room temperature and poured into 1.5 L of water. Theresulting solid was filtered and dried under vacuum at 40° C. overnight.The crude product was divided into two parts, one of which was enrichedvia chromatography on silica gel (200 g) and the other using an AnaLogixcolumn (220 g). The combined fractions (15.1 g, 45 mmol, 1 eq.) weredissolved in trifluoroacetic acid (450 mL) and treated with bromine(2.52 mL, 49 mmol, 1.1 eq.) at 65° C. for 4 hours. The reaction wascooled to room temperature and poured into water (6 L). The solid wasfiltered and triturated with acetonitrile (550 mL). The filtered solidwas dried in a convection oven at 40° C. overnight to give compound (B)(13.6 g, 84%) as a yellow orange solid which was used subsequently.

3-(5-(2H-Benzo[d][1,2,3]triazol-2-yl)-6-hydroxy-[1,1′-biphenyl]-3-yl)-propanoicacid (C)

A solution of compound (B) (13.6 g, 37.6 mmol, 1 eq.), phenylboronicacid (9.16 g, 75.1 mmol, 2 eq.), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.7 g, 2.3 mmol, 0.06 eq.), and potassiumcarbonate (25.9 g, 188 mmol, 5 eq.) in dioxane (200 mL) and water (70mL) was heated to 90° C. for 7 hours. The reaction was diluted withethyl acetate (500 mL) and filtered through Celite (25 g). The filtratewas diluted with ethyl acetate (500 mL) and water (1 L). The organiclayer was separated and washed with saturated brine (500 mL) andconcentrated under reduced pressure. The residue was purified oversilica gel (400 g) eluting with a gradient of 0 to 75% tetrahydrofuranin heptanes. The material was triturated with methyl tert-butyl ether(150 mL). Final purification on an AnaLogix Reverse Phase column (300 g)eluting with a gradient of 0 to 100% of 9:1 methanol:tetrahydrofuran inwater. The solid was triturated with diethyl ether (20 mL) to givecompound (C) (4.9 g, 36%) as a white solid. ¹H NMR (300 MHz, DMSO-d₆) δ8.09 (dd, 2H), 8.04 (d, 1H), 7.61 (m, 4H), 7.48 (m, 2H), 7.39 (m, 2H),2.94 (t, 2H), 2.64 (t, 2H).

2-((3-(5-(2H-benzo[d][1,2,3]triazol-2-yl)-6-hydroxy-[1,1′-biphenyl]-3-yl)propanoyl)oxy)-ethylmethacrylate (D)

Compound (C) (100 mg, 0.278 mmol), 150 mg of 2-hydroxyethyl methacrylate(1.15 mmol), and 10 mg of N,N-dimethylaminopyridine (catalyst) werestirred in 10 mL of dichloromethane at room temperature under a nitrogenatmosphere. Diisopropyl carbodiimide (100 mg, 0.79 mmol) was added tothe mixture while constantly stirring the system at room temperature.The consumption of the carboxylic acid was monitored by thin layerchromatography. Once the reaction was complete, the volatiles wereevaporated under reduced pressure, and compound (D) was purified byflash chromatography using ethyl acetate and hexanes as the solvents. ¹HNMR (500 MHz, CDCl₃) δ 11.7 (s, 1H), 8.25 (m, 1H), 7.9 (m, 2H), 7.65 (d,2H), 7.45 (m, 4H), 7.35 (m, 1H), 7.25 (d, 1H), 6.05 (t, 1H), 5.5 (t,1H), 4.3 (m, 4H), 3.05 (t, 2H), 2.7 (t, 2H), 1.8 (s, 3H).

Example 2—Synthesis Compound (K) as Shown in Scheme 3

2-bromo-4-(tert-butyl)-6-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)phenol(F)

Bromine (14.4 mL, 280 mmol, 2 eq.) was added dropwise to a solution ofcompound (E) (50.0 g, 140 mmol) in 1.5 L of trifluoroacetic acid and themixture was heated to 65° C. for two hours. The mixture was cooled toroom temperature and poured into 2 L of water. The resultant solid wasfiltered, washed with an additional 1 L of water, and dried under vacuumat 40° C. overnight to yield compound (F) (52.6 grams, 99%) as an offwhite solid.

Methyl3-(5′-(tert-butyl)-3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanoate(H)

A solution of compound (F) (14.5 g, 38.1 mmol),4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (14.5 g,57.1 mmol, 1.5 eq.), and potassium acetate (11.2 g, 114 mmol, 3 eq.) in290 mL of dioxane was sparged with nitrogen for 10 minutes.[1,1′-bis(diphenylphosphino)ferrocene] dichloropalladium(II) (2.5 g, 3.4mmol, 9 mole %) was added and the mixture was heated at 80° C. for fourhours, at which point, the reaction appeared complete by liquidchromatography. The mixture was then treated withbis(triphenylphosphine)palladium(II) chloride (1.2 g, 1.7 mmol, 5 mole%), potassium carbonate (14.4 g, 104 mmol, 2.7 eq.), methyl3-(4-iodophenyl) propionate (10.0 g, 34.6 mmol, 0.9 eq.) and water (78mL), and heated to 80° C. for four hours before stirring overnight atroom temperature.

The mixture was diluted with 1.2 L of ethyl acetate and washed with 2.1L of water. The organic layer was filtered through a celite pad (150 g),which was rinsed with an additional 500 mL of ethyl acetate. Thefiltrate was dried over sodium sulfate, filtered, and concentrated underreduced pressure. The residue was chromatographed over silica gel usingethyl acetate and hexanes to provide compound (H) as a pale yellow solid(7.3 g, 46%). ¹H NMR (300 MHz, CDCl₃) δ 11.40 (s, 1H), 8.40 (d, 1H),7.93 (d, 1H), 7.88 (d, 1H), 7.59 (d, 2H), 7.43 (m, 2H), 7.32 (d, 2H),3.71 (s, 3H), 3.03 (t, 2H), 2.71 (t, 2H), 1.42 (s, 9H).

Methyl3-(3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanoate(I)

A solution of compound (H) (2.1 g, 4.5 mmol), anhydrous aluminumchloride (1.3 g, 10 mmol, 2.2. eq.) and nitromethane (1.2 g, 20 mmol,4.4 eq.) in 35 mL of toluene was heated and stirred overnight at 55° C.Additional aluminum chloride (0.3 g, 2.3 mmol, 0.5 eq.) was added andheating continued for 18 more hours, after which, the reaction wascooled and combined with crude product mixtures from three otherpreviously performed experiments. The combined mixture was diluted with200 mL of ethyl acetate. The organics were washed with water (200 mL),after which the aqueous portion was extracted with a 1:1 mixture ofethyl acetate and tetrahydrofuran (120 mL), and the combined organicswere concentrated under reduced pressure.

The residue was purified on an AnaLogix column (120 g) eluting with agradient of 0-100% ethyl acetate in heptanes. The material wasre-purified on an AnaLogix reverse phase column (275 g) eluting with agradient of 0-100% tetrahydrofuran in water. The crude product wastriturated with 20 mL of methyl tert-butyl ether to give compound (I) asan off white solid. ¹H NMR (300 MHz, CDCl₃) δ 11.40 (s, 1H), 8.40 (dd,1H), 7.93 (d, 1H), 7.88 (d, 1H), 7.59 (d, 2H), 7.43 (dt, 2H), 7.32 (d,2H), 7.12 (t, 1H), 3.71 (s, 3H), 3.03 (t, 2H), 2.71 (t, 2H).

2-(3-(3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanamido)ethylmethacrylate (K)

Compound (I) (500 mg, 1.23 mmol), 50 mg of anhydrous sodium carbonate(catalytic), and 500 mg of 2-aminoethanol (excess) were stirred in 10 mLof anhydrous methanol under a nitrogen atmosphere at 60° C. for 24 hrs.The mixture was cooled to room temperature, and poured into 50 mL ofdeionized water. The precipitate that formed was filtered over a frittedglass funnel and washed two times with 50 mL of deionized water, afterwhich it was dried in a rotary evaporator, followed by drying in avacuum oven at 50° C., yielding compound (J).

100 mg of the hydroxyamide (J) (0.229 mmol), 250 mg of methacrylic acid(2.9 mmol), and 20 mg of N,N-dimethylaminopyridine (catalytic) werestirred in 20 mL of CH₂Cl₂ and heated to a gentle reflux to dissolve thestarting material. Ethyl dimethylaminopropyl carbodiimide hydrochloride(EDC, 100 mg, ˜0.52 mmol) was added to the solution, and the mixture wasallowed to stir while refluxing until all of the starting material wasconsumed. The methylene chloride was evaporated under reduced pressure,after which the organics were dissolved in 150 mL of ethyl acetate. Themixture was extracted with 100 mL of 1 N HCl, followed by deionizedwater. The excess methacrylic acid was then removed by washing theorganics with 50 mL of aqueous sodium carbonate, followed by washing twotimes with 50 mL of deionized water. The organics were dried on a rotaryevaporator and washed with hexanes over a fritted glass funnel, yielding(K). ¹H NMR (500 MHz, CDCl₃): δ 11.55 (s, 1H), 8.35 (d, 1H), 7.2-8.1 (m,8H), 7.1 (t, 1H), 6.1 (s, 1H), 5.55 (s, 1H), 4.2 (t, 2H), 3.65 (m, 2H),3.0 (m, 2H), 2.5 (m, 2H), 1.9 (s, 3H).

Example 3—Synthesis of Compound (M) as Shown in Scheme 32-(3-(5′-(tert-butyl)-3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanamido)ethylmethacrylate (M)

A suspension of compound (H) (1.0 g, 2.16 mmol), 1.0 g sodium carbonate,and 2.0 g of ethanolamine (32.8 mmol) in 25 mL of anhydrous methanol washeated to 65° C. in a round bottom flask equipped with a magneticstirrer and reflux condenser under a nitrogen environment. Progress ofthe reaction was monitored by thin layer chromatograph (TLC), whichshowed complete consumption of compound (H) after 20 hours, and theformation of the amidoethyl alcohol derivative (L) as the sole product.The mixture was cooled to room temperature, and the methanol evaporatedunder reduced pressure. The residual material was treated with diluteaqueous HCl, adjusted to a final pH of ˜6.5, and stirred for anadditional 30 minutes at room temperature. The resulting solids werefiltered over a fritted glass funnel and washed with deionized waterprior to drying in a vacuum oven at 50° C.

A solution of the dried amidoethyl alcohol (L) (500 mg, 1.01 mmol) and500 mg of methacrylic anhydride (3.25 mmol. 3.22 eq.) in 10 mL ofanhydrous acetonitrile was heated at 83° C. in a round bottom flaskequipped with a magnetic stirrer and reflux condenser. The reaction wasmonitored by TLC and appeared complete after 24 hours, after which themixture was cooled to room temperature and all volatiles evaporatedunder reduced pressure. The mixture was redissolved in ethyl acetate,extracted with aqueous sodium carbonate, concentrated under reducedpressure, and purified by chromatography over silica gel using ethylacetate and dichloromethane. Evaporation of the solvents under reducedpressure gave compound (M). ¹H NMR (500 MHz, CDCl₃) δ 11.36 (s, 1H),8.40 (d, 1H), 7.90 (d, 1H), 7.86 (d, 1H), 7.55 (d, 2H), 7.41 (m, 2H),7.28 (d, 2H), 6.08 (s, 1H), 5.75 (bs, 1H), 5.55 (s, 1H), 4.20 (t, 2H),3.55 (dd, 2H), 3.01 (t, 2H), 2.53 (t, 2H), 1.90 (s, 3H), 1.39 (s, 9H).

FIG. 1 shows the UV-VIS transmission spectra of 0.2 mM solutions ofNorbloc®, compound (D), and compound (K) in methanol. Both compounds (D)and (K) are more effective than Norbloc® at absorbing UV light in therange of 250-280 nm and exhibit bathochromic shifts of about 10 nm incomparison to Norbloc® in the range of 360-400 nm.

FIG. 2 shows the UV-VIS transmission spectra of Norbloc® (0.2 mMmethylene chloride), and of compound (M) (0.2 mM and 1 mM in methylenechloride). Compound (M) is more effective than Norbloc® at absorbing UVlight in the range of 250-280 nm and exhibits a bathochromic shift ofabout 20-30 nm in comparison to Norbloc® in the range of 360-400 nm,depending on concentration.

Example 4—Silicone Hydrogel Formulations

Master Batch: A 300 gram master batch of a reactive monomer mixture wasprepared composed of 77 weight percent of the formulation listed inTable 5 and 23 weight percent of the diluent D3O. All of the componentsexcept the PVP were mixed in a jar under a nitrogen atmosphere at 29° C.for 90 minutes, after which the PVP was added and mixed for anadditional 240 minutes at 30° C. Thereafter, the jar was capped andplaced on a roller for 1050 minutes at room temperature. The reactivemonomer mixture was then filtered through a 3 μm filter using astainless steel syringe under pressure.

TABLE 5 Base Formulation Component (weight %) mPDMS 1000 31.6 SiMAA 28.6DMA 24.5 HEMA 6.13 TEGDMA 1.53 PVP K90 7.14 Irgacure 1870 0.35 Irgacure184 0.15 Σ Components 100

Formulation 4A—401.6 milligrams of compound (M) were dissolved in 14.61grams of the Master Batch under a nitrogen atmosphere, thereby producinga reactive monomer mixture containing 3.47 weight percent or 0.619 molepercent of compound (M).

Formulation 4B—230.6 milligrams of Norbloc® were dissolved in 14.76grams of the Master Batch under a nitrogen atmosphere, thereby producinga reactive monomer mixture containing 2.00 weight percent or 0.619 molepercent of Norbloc®.

Lens Fabrication—Formulation 4A or 4B was degassed at ambienttemperature by applying vacuum (40 torr) for 45 minutes. Then, in aglove box with a nitrogen gas atmosphere and less than about 0.1-0.2percent oxygen gas, about 75-100 μL of the reactive mixture were dosedusing an Eppendorf pipet at room temperature into the FC made of Zeonor.The BC made of 90:10 Z:TT was then placed onto the FC. The molds wereequilibrated for a minimum of twelve hours in the glove box prior todosing. Trays containing eight mold assemblies each were transferredinto an adjacent glove box maintained at 65° C., and the lenses werecured from the top and the bottom for 20 minutes using 435 nm LED lightshaving an intensity of about 2 mW/cm² at the tray's location. The LEDlight sources were about 10 inches away from the trays.

The lenses were manually de-molded with most lenses adhering to the FCand released by suspending the lenses in about one liter of 70 percentIPA for about one or two hours, followed by washing two times with 70percent IPA and then three times with DI water. Each washing step lastedabout 30 minutes. The lenses were equilibrated in borate bufferedpackaging solution overnight and then stored in fresh borate bufferedpackaging solution thereafter. A person of ordinary skill recognizesthat the exact lens release process can be varied depending on the lensformulation and mold materials, regarding the concentrations of theaqueous isopropanol solutions, the number of washings with each solvent,and the duration of each step. The purpose of the lens release processis to release all of the lenses without defects and transition fromdiluent swollen networks to the packaging solution swollen hydrogels.

The center thickness of the lenses was measured; formulation 4A had acenter thickness of 88 microns, while formulation 4B has a centerthickness of 89 microns. Since the center thicknesses are almostidentical, the UV-VIS spectra of lenses made from these two formulationshaving equimolar amounts of either compound (M) or Norbloc® may becompared, and the observed differences may be rationally assumed to becaused by the different chemical structures and not their concentrationor path length through any lens.

FIG. 3 shows the UV-VIS spectra of the lenses made from Formulation 4Aand 4B. Formulation 4A containing compound (M) was more effective thanFormulation 4B containing Norbloc® at absorbing UV light in the range of250-280 nm, and Formulation 4A exhibited a bathochromic shift of about20 nm as compared to Formulation 4B in the range of 360-400 nm.

We claim:
 1. A compound selected from:2-(3-(5-(2H-benzo[d][1,2,3]triazol-2-yl)-6-hydroxy-[1,1′-biphenyl]-3-yl)propanamido)ethylmethacrylate,2-(3-(3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanamido)ethylmethacrylate, and2-(3-(5′-(tert-butyl)-3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanamido)ethylmethacrylate.
 2. An ophthalmic device comprising a free radical reactionproduct of: a compound of formula I:

wherein: R¹ at each occurrence is independently H, halo, amino, orhydroxyl; and at least one of R² or R³ is a group of formula R_(g)-L,wherein R_(g) is a polymerizable group and L is a linking group, and theremaining R² and R³ are independently at each occurrence R_(g)-L, H,C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₃-C₇ cycloalkyl, wherein each alkyl andcycloalkyl may be unsubstituted or substituted; and one or more monomerssuitable for making the ophthalmic device.
 3. The ophthalmic device ofclaim 2 wherein the monomer suitable for making the ophthalmic devicecomprises a hydrophilic monomer, a silicone-containing component, ormixtures thereof.
 4. The ophthalmic device of claim 2 that is a contactlens, a corneal onlay, a corneal inlay, an intraocular lens, or anoverlay lens.
 5. A hydrogel formed from a reactive mixture comprising: acompound of formula I:

wherein: R¹ at each occurrence is independently H, halo, amino, orhydroxyl; and at least one of R² or R³ is a group of formula R_(g)-L,wherein R_(g) is a polymerizable group and L is a linking group, and theremaining R² and R³ are independently at each occurrence R_(g)-L, H,C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₃-C₇ cycloalkyl, wherein each alkyl andcycloalkyl may be unsubstituted or substituted; and one or more monomerssuitable for making the hydrogel.
 6. The hydrogel of claim 5 wherein themonomer suitable for making the hydrogel comprises a hydrophilicmonomer, a silicone-containing component, or mixtures thereof.
 7. Thehydrogel of claim 5 wherein the monomer suitable for making the hydrogelcomprises a hydrophilic monomer and a silicone-containing component. 8.A contact lens comprising the hydrogel of claim
 5. 9. A method formaking the ophthalmic device of claim 2, the method comprising: (a)providing a reactive mixture containing the compound of formula I, oneor more monomers, and a radical initiator; and (b) polymerizing thereactive mixture to form the ophthalmic device.
 10. A compositionselected from:3-(5-(2H-benzo[d][1,2,3]triazol-2-yl)-6-hydroxy-[1,1′-biphenyl]-3-yl)propanoicacid, methyl3-(3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanoate,and methyl3-(5′-(tert-butyl)-3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanoate.11. The ophthalmic device of claim 2 wherein R¹ is at each occurrence isindependently H or halo.
 12. The ophthalmic device of claim 2 wherein R²and R³ at each occurrence are independently H, C₁-C₆ alkyl, or Rg-L. 13.The ophthalmic device of claim 2 wherein Rg comprises styryl, vinylcarbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinylamide,(meth)acrylate, or (meth)acrylamide.
 14. The ophthalmic device of claim2 wherein the linking group comprises C₁-C₈ alkylene, C₁-C₈ oxaalkylene,C₁-C₈ thiaalkylene, C₁-C₈ alkylene-carboxylate-C₁-C₈ alkylene, C₁-C₈alkylene-amide-C₁-C₈ alkylene, or C₁-C₈ alkylene-amine-C₁-C₈ alkylene.15. The ophthalmic device of claim 2 wherein the compound of formula Iis selected from:2-(3-(5-(2H-benzo[d][1,2,3]triazol-2-yl)-6-hydroxy-[1,1′-biphenyl]-3-yl)propanamido)ethylmethacrylate,2-(3-(3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanamido)ethylmethacrylate, and2-(3-(5′-(tert-butyl)-3′-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2′-hydroxy-[1,1′-biphenyl]-4-yl)propanamido)ethylmethacrylate.